Si-containing film forming compositions and methods of making and using the same

ABSTRACT

Si-containing film forming compositions are disclosed comprising a precursor having the formula [—NR—R4R5Si—(CH2)t—SiR2R3—]n wherein n=2 to 400; R, R2, R3, R4, and R5 are independently H, a hydrocarbon group, or an alkylamino group, and provided that at least one of R2, R3, R4, and R5 is H; and R is independently H, a hydrocarbon group, or a silyl group. Exemplary precursors include, but are not limited to, [—NH—SiH2—CH2—SiH2—]n, and [—N(SiH2—CH2—SiH3)—SiH2—CH2—SiH2—]n.

CROSS REFERENCE TO RELATED APPLICATIONS

The present application claims the benefit of U.S. provisional patentapplication No. 62/312,352 filed Mar. 23, 2016, herein incorporated byreference in its entirety for all purposes.

TECHNICAL FIELD

Si-containing film forming compositions are disclosed comprisingprecursors containing a unit having the following formula:

[—NR—R⁴R⁵Si—(CH₂)_(t)—SiR²R³—]_(n)   (II)

wherein m=1 to 4; t=1 to 4; n=2 to 400; R², R³, R⁴, and R⁵ areindependently H, a C₁ to C₆ hydrocarbon, or an alkylamino group havingthe formula NR″₂ and each R″ is independently H, a C₁-C₆ hydrocarbon, aC₆-C₁₂ aryl, or NR″₂ forms a cyclic amine group, and provided that atleast one of R², R³, R⁴, and R⁵ is H; and R is H; a C₁-C₆ hydrocarbon; asilyl group having the formula Si_(x)R′_(2x+1), with x=1 to 4 and eachR′ independently ═H, a C₁-C₆ hydrocarbon group, or an alkylamino grouphaving the formula NR″₂ and each R″ independently H, a C₁-C₆ group, aC₆-C₁₂ aryl, or NR″₂ forms a cyclic amine group; or aR^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group, with b=1 to 2 andR^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) are independently a H, aC₁-C₆ hydrocarbon, a C₆-C₁₂ aryl, or an alkylamino group having theformula NR″₂ and each R″ is independently H, a C₁-C₆ group, a C₆-C₁₂aryl, or NR″₂ forms a cyclic amine group; and provided that at least oneof R^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) is H.

BACKGROUND

Si-containing films are used widely in the semiconductor, photovoltaic,LCD-TFT, flat panel-type device, refactory material, or aeronauticindustries. Si-containing films may be used, for example, as dielectricmaterials having electrical properties which may be insulating (SiO₂,SiN, SiC, SiCN, SiCOH, MSiO_(x), wherein M is Hf, Zr, Ti, Nb, Ta, or Geand x is 0-4). Si-containing films may also be used as conducting films,such as metal silicides or metal silicon nitrides. Due to the strictrequirements imposed by downscaling of electrical device architecturestowards the nanoscale (especially below 28 nm node), increasinglyfine-tuned molecular precursors are required which meet the requirementsof volatility (for vapor deposition processes), lower processtemperatures, reactivity with various oxidants and low filmcontamination, in addition to high deposition rates, conformality andconsistency of films produced.

Hizawa and Nojimoto (Kogyo Kagaku Zasshi, 1956, 59, 1359-63) describethe synthesis of (Me₃SiCH₂SiMe₂)₂NH from the reaction of Me₃SiCH₂SiMe₂Cland NH₃.

O'Neill et al. (U.S. Pat. App. Pub. No. 2015/0087139) disclose fiveclasses of organoaminosilane precursors, includingH₃Si—R³—SiH₂—NR¹—SiH₂—R³—SiH₃, wherein R¹ is a linear or branched C₁ toC₁₂ hydrocarbon group, a linear or branched C₃ to C₁₂ alkenyl group, alinear or branched C₃ to C₁₂ alkynyl group, a C₃ to C₁₂ cyclic alkylgroup, or a C₅ to C₁₂ aryl group and R³ is a linear or branched C₁ toC₁₂ alkylene group, a linear or branched C₃ to C₆ alkynylene group, a C₃to C₁₂ cyclic alkylene group, a C₃ to C₁₂ hetero-cyclic alkylene group,a C₅ to C₁₂ arylene group, or a C₅ to C₁₂ hetero arylene group.

WO2016/049154 to Fafard et al. discloses carbosilane substituted amineprecursors for deposition of Si-containing films. The carbosilanesubstituted amine precursors have the formula(R¹)_(a)N(—SiHR²—CH₂—SiH₂R³)_(3-a), wherein a=0 or 1; R¹ is H a C1 to C6alkyl group, or a halogen; R² and R³ is each independently H, a halogen,an alkoxy, or an alkylamino group.

WO2016/160991 to Kerrigan et al. discloses catalytic dehydrogenativecoupling of carbosilanes with ammonia, amines, and amidines.

A need remains to design and produce Si-depositing precursors,especially to design and produce precursors with halogen-free and/ormore selective routes, to provide device engineers the ability to tunemanufacturing process requirements and achieve films with desirableelectrical and physical properties.

SUMMARY

Disclosed are Si-containing film forming compositions comprisingprecursors having the following formula:

R_(a)N(R⁴R⁵Si—(CH₂)_(m)SiR¹R²R³)_(3-a)   (I)

or containing a unit having the following formula:

[—NR—R⁴R⁵Si—(CH₂)_(t)—SiR²R³—]_(n)   (II)

wherein

-   a=0 to 1;-   m=1 to 4;-   t=1 to 4;-   n=2 to 400;-   R¹, R², R³, R⁴, and R⁵ are independently H, a hydrocarbon group (C₁    to C₆), or an alkylamino group having the formula NR″₂ and each R″    is independently H, a C₁-C₆ hydrocarbon group, a C₆-C₁₂ aryl, or    NR″₂ forms a cyclic amine group, and provided that at least one of    R¹, R², R³, R⁴, and R⁵ is H; and-   R is H; a C₁-C₆ hydrocarbon group; a silyl group having the formula    Si_(x)R′_(2x+1) with x=1 to 4 and each R′ independently ═H, a C₁-C₆    hydrocarbon group, or an alkylamino group having the formula NR″₂    and each R″ is independently H, a C₁-C₆ group, a C₆-C₁₂ aryl, or    NR″₂ forms a cyclic amine group; or a    R^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group, wherein b=1 to 2    and R^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) are independently H,    a C₁-C₆ hydrocarbon group, a C₆-C₁₂ aryl, or an alkylamino group    having the formula NR″₂ and each R″ is independently H, a C₁-C₆    group, a C₆-C₁₂ aryl, or NR″₂ forms a cyclic amine group; and    provided that at least one of R^(1′), R^(2′), R^(3′), R^(4′), and    R^(5′) is H. The disclosed Si-containing film forming compositions    may include one or more of the following aspects:    -   m=1 to 2;    -   t=1 to 2;    -   a=0 and m=1;    -   the precursor being N(SiR⁴R⁵(CH₂)SiR¹R²R³)₃;    -   R¹═R²═R³═R⁴═R⁵═H;    -   the precursor being N(—SiH₂—CH₂—SiH₃)₃;    -   at least one of R¹, R², or R³═H;    -   at least one of R⁴ or R⁵═H    -   at least one of R¹, R², or R³ and at least one of R⁴ or R⁵═H;    -   R¹, R², R³ and R⁴═H;    -   at least one of R¹, R², R³, R⁴, or R⁵ being vinyl;    -   at least one of R¹, R², R³, R⁴, or R⁵ being allyl;    -   at least one of R¹, R², R³, R⁴, or R⁵ being phenyl;    -   R², R³, R⁴ and R⁵═H;    -   the precursor being N(SiH₂—CH₂—SiH₂(CH₂═CH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(CH₂═CH—CH₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NH₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NMe₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NMeEt))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NEt₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NnPr₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NiPr₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NBu₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NiBu₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NtBu₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NAm₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NCyPentyl₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(Nhexyl₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NCyHex₂))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NMeH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NEtH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NnPrH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NiPrH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NBuH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NiBuH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NtBuH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(NAmH))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(pyridine))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(pyrrole))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(pyrrolidine))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(imidazole))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(pyrimidine))₃;    -   the precursor being N(SiH₂—CH₂—SiH₂(piperidine))₃;    -   R¹, R² and R³═H;    -   R², R³ and R⁴═H;    -   the precursor being N(SiH(CH₂═CH)—CH₂—SiH₂(CH₂═CH))₃;    -   the precursor being N(SiH(CH₂═CH—CH₂)—CH₂—SiH₂(CH₂═CH—CH₂))₃;    -   the precursor being N(SiH(NH₂)—CH₂—SiH₂(NH₂))₃;    -   the precursor being N(SiH(NMe₂)-CH₂—SiH₂(NMe₂))₃;    -   the precursor being N(SiH(NMeEt)-CH₂—SiH₂(NMeEt))₃;    -   the precursor being N(SiH(NEt₂)-CH₂—SiH₂(NEt₂))₃;    -   the precursor being N(SiH(NnPr₂)-CH₂—SiH₂(NnPr₂))₃;    -   the precursor being N(SiH(NiPr₂)-CH₂—SiH₂(NiPr₂))₃;    -   the precursor being N(SiH(NBu₂)-CH₂—SiH₂(NBu₂))₃;    -   the precursor being N(SiH(NiBu₂)-CH₂—SiH₂(NiBu₂))₃;    -   the precursor being N(SiH(NtBu₂)-CH₂—SiH₂(NtBu₂))₃;    -   the precursor being N(SiH(NAm₂)-CH₂—SiH₂(NAm₂))₃;    -   the precursor being N(SiH(NCyPentyl₂)-CH₂—SiH₂(NCyPentyl₂))₃;    -   the precursor being N(SiH(Nhexyl₂)-CH₂—SiH₂(Nhexyl₂))₃;    -   the precursor being N(SiH(NCyHex₂)-CH₂—SiH₂(NCyHex₂))₃;    -   the precursor being N(SiH(NMeH)—CH₂—SiH₂(NMeH))₃;    -   the precursor being N(SiH(NEtH)—CH₂—SiH₂(NEtH))₃;    -   the precursor being N(SiH(NnPrH)—CH₂—SiH₂(NnPrH))₃;    -   the precursor being N(SiH(NiPrH)—CH₂—SiH₂(NiPrH))₃;    -   the precursor being N(SiH(NBuH)—CH₂—SiH₂(NBuH))₃;    -   the precursor being N(SiH(NiBuH)—CH₂—SiH₂(NiBuH))₃;    -   the precursor being N(SiH(NtBuH)—CH₂—SiH₂(NtBuH))₃;    -   the precursor being N(SiH(NAmH)—CH₂—SiH₂(NAmH))₃;    -   the precursor being N(SiH(pyridine)-CH₂—SiH₂(pyridine))₃;    -   the precursor being N(SiH(pyrrole)-CH₂—SiH₂(pyrrole))₃;    -   the precursor being N(SiH(pyrrolidine)-CH₂—SiH₂(pyrrolidine))₃;    -   the precursor being N(SiH(imidazole)-CH₂—SiH₂(imidazole))₃;    -   the precursor being N(SiH(piperidine)-CH₂—SiH₂(imidazole))₃;    -   the precursor being N(SiH(pyrimidine)-CH₂—SiH₂(imidazole))₃;    -   R³, R⁴ and R⁵═H;    -   the precursor being N(SiH₂—CH₂—SiH(CH₂═CH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NH₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NMe₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NMeEt)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NEt₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NnPr₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NiPr₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NBu₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NiBu₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NtBu₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NAm₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NCyPentyl₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(Nhexyl₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NCyHex₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NMeH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NEtH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NnPrH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NiPrH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NBuH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NiBuH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NtBuH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(NAmH)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(pyridine)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(pyrrole)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(pyrrolidine)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(imidazole)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(piperidine)₂)₃;    -   the precursor being N(SiH₂—CH₂—SiH(pyrimidine)₂)₃;    -   R⁴ and R⁵═H;    -   the precursor being N(SiH₂—CH₂—Si—(CH₂═CH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NH₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NMe₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NMeEt)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NEt₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NnPr₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NiPr₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NBu₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NiBu₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NtBu₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NAm₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NCyPentyl₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(Nhexyl₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NCyHex₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NMeH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NEtH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NnPrH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NiPrH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NBuH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NiBuH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NtBuH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(NAmH)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(pyridine)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(pyrrole)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(pyrrolidine)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(imidazole)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(piperidine)₃)₃;    -   the precursor being N(SiH₂—CH₂—Si(pyrimidine)₃)₃;    -   a=0 and m=2;    -   the precursor being N(SiR⁴R⁵(CH₂CH₂)SiR¹R²R³)₃;    -   R¹, R², R³, R⁴ and R⁵═H;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₃)₃;    -   R¹, R², R³ and R⁴═H;    -   R², R³, R⁴ and R⁵═H;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NH₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NMe₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NMeEt))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NEt₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NnPr₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NiPr₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NBu₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NiBu₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NtBu₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NAm₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NCyPentyl₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(Nhexyl₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NCyHex₂))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NMeH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NEtH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NnPrH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NiPrH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NBuH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NiBuH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NtBuH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(NAmH))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(pyridine))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(pyrrole))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(pyrrolidine))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(imidazole))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(piperidine))₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH₂(pyrimidine))₃;    -   R¹, R² and R³═H;    -   R², R³ and R⁴═H;    -   the precursor being N(SiH(CH₂═CH)—CH₂—CH₂—SiH₂(CH₂═CH))₃;    -   the precursor being        N(SiH(CH₂═CH—CH₂)—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₃;    -   the precursor being N(SiH(NH₂)—CH₂—CH₂—SiH₂(NH₂))₃;    -   the precursor being N(SiH(NMe₂)-CH₂—CH₂—SiH₂(NMe₂))₃;    -   the precursor being N(SiH(NMeEt)-CH₂—CH₂—SiH₂(NMeEt))₃;    -   the precursor being N(SiH(NEt₂)-CH₂—CH₂—SiH₂(NEt₂))₃;    -   the precursor being N(SiH(NnPr₂)-CH₂—CH₂—SiH₂(NnPr₂))₃;    -   the precursor being N(SiH(NiPr₂)-CH₂—CH₂—SiH₂(NiPr₂))₃;    -   the precursor being N(SiH(NBu₂)-CH₂—CH₂—SiH₂(NBu₂))₃;    -   the precursor being N(SiH(NiBu₂)-CH₂—CH₂—SiH₂(NiBu₂))₃;    -   the precursor being N(SiH(NtBu₂)-CH₂—CH₂—SiH₂(NtBu₂))₃;    -   the precursor being N(SiH(NAm₂)-CH₂—CH₂—SiH₂(NAm₂))₃;    -   the precursor being        N(SiH(NCyPentyl₂)-CH₂—CH₂—SiH₂(NCyPentyl₂))₃;    -   the precursor being N(SiH(Nhexyl₂)-CH₂—CH₂—SiH₂(Nhexyl₂))₃;    -   the precursor being N(SiH(NCyHex₂)-CH₂—CH₂—SiH₂(NCyHex₂))₃;    -   the precursor being N(SiH(NMeH)—CH₂—CH₂—SiH₂(NMeH))₃;    -   the precursor being N(SiH(NEtH)—CH₂—CH₂—SiH₂(NEtH))₃;    -   the precursor being N(SiH(NnPrH)—CH₂—CH₂—SiH₂(NnPrH))₃;    -   the precursor being N(SiH(NiPrH)—CH₂—CH₂—SiH₂(NiPrH))₃;    -   the precursor being N(SiH(NBuH)—CH₂—CH₂—SiH₂(NBuH))₃;    -   the precursor being N(SiH(NiBuH)—CH₂—CH₂—SiH₂(NiBuH))₃;    -   the precursor being N(SiH(NtBuH)—CH₂—CH₂—SiH₂(NtBuH))₃;    -   the precursor being N(SiH(NAmH)—CH₂—CH₂—SiH₂(NAmH))₃;    -   the precursor being N(SiH(pyridine)-CH₂—CH₂—SiH₂(pyridine))₃;    -   the precursor being N(SiH(pyrrole)-CH₂—CH₂—SiH₂(pyrrole))₃;    -   the precursor being        N(SiH(pyrrolidine)-CH₂—CH₂—SiH₂(pyrrolidine))₃;    -   the precursor being N(SiH(imidazole)-CH₂—CH₂—SiH₂(imidazole))₃;    -   the precursor being        N(SiH(piperidine)-CH₂—CH₂—SiH₂(piperidine))₃;    -   the precursor being        N(SiH(pyrimidine)-CH₂—CH₂—SiH₂(pyrimidine))₃;    -   R³, R⁴ and R⁵═H;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(CH₂═CH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NH₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NMe₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NMeEt)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NEt₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NnPr₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NiPr₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NBu₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NiBu₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NtBu₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NAm₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NCyPentyl₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(Nhexyl₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NCyHex₂)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NMeH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NEtH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NnPrH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NiPrH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NBuH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NiBuH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NtBuH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(NAmH)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(pyridine)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(pyrrole)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(pyrrolidine)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(imidazole)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(piperidine)₂)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—SiH(pyrimidine)₂)₃;    -   R⁴ and R⁵═H;    -   the precursor being N(SiH₂—CH₂—CH₂—Si—(CH₂═CH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NH₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NMe₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NMeEt)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NEt₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NnPr₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NiPr₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NBu₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NiBu₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NtBu₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NAm₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NCyPentyl₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(Nhexyl₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NCyHex₂)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NMeH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NEtH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NnPrH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NiPrH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NBuH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NiBuH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NtBuH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(NAmH)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(pyridine)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(pyrrole)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(pyrrolidine)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(imidazole)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(piperidine)₃)₃;    -   the precursor being N(SiH₂—CH₂—CH₂—Si(pyrimidine)₃)₃;    -   a=1 and m=1;    -   the precursor being RN(SiR⁴R⁵(CH₂)SiR¹R²R³)₂;    -   R, R¹, R², R³, R⁴ and R⁵═H;    -   the precursor being HN(SiH₂—CH₂—SiH₃)₂;    -   at least one of R, R¹, R², R³, R⁴, or R⁵ being vinyl;    -   at least one of R, R¹, R², R³, R⁴, or R⁵ being allyl;    -   at least one of R, R¹, R², R³, R⁴, or R⁵ being phenyl;    -   R¹, R², R³, R⁴ and R⁵═H and R═Si_(x)H_(2x+1) (x=1 to 4);    -   the precursor being SiH₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si₂H₅N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si₃H₇N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si₄H₉N(SiH₂—CH₂—SiH₃)₂;    -   R¹, R², R³, R⁴ and R⁵═H and R═C_(y)H_(2y+1) (y=1 to 6);    -   the precursor being (Me)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (Et)N(SiH₂—CH₂—SiH₃)₂    -   the precursor being (nPr)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (iPr)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (Bu)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (iBu)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (tBu)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (amyl)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (hexyl)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiMe₃)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiEt₃)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si(iPr)₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si(nPr)₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si(Bu)₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si(iBu)₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si(tBu)₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si(amyl)₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being Si(hexyl)₃N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiHMe₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiHEt₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(iPr)₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(nPr)₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(Bu)₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(iBu)₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(tBu)₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(amyl)₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(hexyl)₂N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂MeN(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂EtN(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(iPr)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(nPr)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(Bu)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(iBu)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(tBu) N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(amyl)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(hexyl)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₃—CH₂—CH₂—SiH₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiMe₃-CH₂—SiMe₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiMe₃-CH₂—CH₂—SiMe₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiEt₃-CH₂—SiEt₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiEt₃-CH₂—CH₂—SiEt₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NMe₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NEt₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NMeEt)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH(NMe₂)₂)N(SiH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH(NEt₂)₂)N(SiH₂—CH₂—SiH₃)₂;    -   R¹, R², R³ and R⁴═H and R═H, C_(u)H_(2u+1), or Si_(v)H_(2v-1),        wherein u=1-6 and v=1-4;    -   R², R³, R⁴ and R⁵═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1),        wherein u=1-6 and v=1-4;    -   the precursor being RN(SiH₂—CH₂—SiH₂(CH₂═CH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(CH₂═CH—CH₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NH₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NMe₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NMeEt))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NEt₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NnPr₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NiPr₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NBu₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NiBu₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NtBu₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NAm₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NCyPentyl₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(Nhexyl₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NCyHex₂))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NMeH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NEtH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NnPrH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NiPrH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NBuH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NiBuH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NtBuH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(NAmH))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(pyridine))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(pyrrole))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(pyrrolidine))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(imidazole))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(piperidine))₂;    -   the precursor being RN(SiH₂—CH₂—SiH₂(pyrimidine))₂;    -   R¹, R² and R³═H and R═H, C_(u)H_(2u+1), SivH_(2v-1), wherein        u=1-6 and v=1-4;    -   R², R³ and R⁴═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1), wherein        u=1-6 and v=1-4;    -   the precursor being RN(SiH(CH₂═CH)—CH₂—SiH₂(CH₂═CH))₂;    -   the precursor being RN(SiH(CH₂═CH—CH₂)—CH₂—SiH₂(CH₂═CH—CH₂))₂;    -   the precursor being RN(SiH(NH₂)—CH₂—SiH₂(NH₂))₂;    -   the precursor being RN(SiH(NMe₂)-CH₂—SiH₂(NMe₂))₂;    -   the precursor being RN(SiH(NMeEt)-CH₂—SiH₂(NMeEt))₂;    -   the precursor being RN(SiH(NEt₂)-CH₂—SiH₂(NEt₂))₂;    -   the precursor being RN(SiH(NnPr₂)-CH₂—SiH₂(NnPr₂))₂;    -   the precursor being RN(SiH(NiPr₂)-CH₂—SiH₂(NiPr₂))₂;    -   the precursor being RN(SiH(NBu₂)-CH₂—SiH₂(NBu₂))₂;    -   the precursor being RN(SiH(NiBu₂)-CH₂—SiH₂(NiBu₂))₂;    -   the precursor being RN(SiH(NtBu₂)-CH₂—SiH₂(NtBu₂))₂;    -   the precursor being RN(SiH(NAm₂)-CH₂—SiH₂(NAm₂))₂;    -   the precursor being RN(SiH(NCyPentyl₂)-CH₂—SiH₂(NCyPentyl₂))₂;    -   the precursor being RN(SiH(Nhexyl₂)-CH₂—SiH₂(Nhexyl₂))₂;    -   the precursor being RN(SiH(NCyHex₂)-CH₂—SiH₂(NCyHex₂))₂;    -   the precursor being RN(SiH(NMeH)—CH₂—SiH₂(NMeH))₂;    -   the precursor being RN(SiH(NEtH)—CH₂—SiH₂(NEtH))₂;    -   the precursor being RN(SiH(NnPrH)—CH₂—SiH₂(NnPrH))₂;    -   the precursor being RN(SiH(NiPrH)—CH₂—SiH₂(NiPrH))₂;    -   the precursor being RN(SiH(NBuH)—CH₂—SiH₂(NBuH))₂;    -   the precursor being RN(SiH(NiBuH)—CH₂—SiH₂(NiBuH))₂;    -   the precursor being RN(SiH(NtBuH)—CH₂—SiH₂(NtBuH))₂;    -   the precursor being RN(SiH(NAmH)—CH₂—SiH₂(NAmH))₂;    -   the precursor being RN(SiH(pyridiHNe)—CH₂—SiH₂(pyridiHNe))₂;    -   the precursor being RN(SiH(pyrrole)-CH₂—SiH₂(pyrrole))₂;    -   the precursor being        RN(SiH(pyrrolidiHNe)—CH₂—SiH₂(pyrrolidiHNe))₂;    -   the precursor being RN(SiH(imidazole)-CH₂—SiH₂(imidazole))₂;    -   the precursor being RN(SiH(piperidine)-CH₂—SiH₂(piperidine))₂;    -   the precursor being RN(SiH(pyrimidine)-CH₂—SiH₂(pyrimidine))₂;    -   R³, R⁴ and R⁵═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1), wherein        u=1-6 and v=1-4;    -   the precursor being RN(SiH₂—CH₂—SiH(CH₂═CH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NH₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NMe₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NMeEt)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NEt₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NnPr₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NiPr₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NBu₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NiBu₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NtBu₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NAm₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NCyPeHNtyl₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(Nhexyl₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NCyHex₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NMeH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NEtH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NnPrH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NiPrH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NBuH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NiBuH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NtBuH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(NAmH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(pyridiHNe)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(pyrrole)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(pyrrolidiHNe)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(imidazole)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(piperidine)₂)₂;    -   the precursor being RN(SiH₂—CH₂—SiH(pyrimidine)₂)₂;    -   R⁴ and R⁵═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1), wherein        u=1-6 and v=1-4;    -   the precursor being RN(SiH₂—CH₂—Si—(CH₂═CH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NH₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NMe₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NMeEt)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NEt₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NnPr₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NiPr₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NBu₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NiBu₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NtBu₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NAm₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NCyPeHNtyl₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(Nhexyl₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NCyHex₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NMeH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NEtH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NnPrH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NiPrH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NBuH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NiBuH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NtBuH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(NAmH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(pyridiHNe)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(pyrrole)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(pyrrolidiHNe)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(imidazole)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(piperidine)₃)₂;    -   the precursor being RN(SiH₂—CH₂—Si(pyrimidine)₃)₂;    -   a=1 and m=2;    -   the formula (I) being RN(SiR⁴R⁵(CH₂)₂SiR¹R²R³)₂;    -   R, R¹, R², R³, R⁴ and R⁵═H;    -   the precursor being HN(SiH₂—CH₂—CH₂—SiH₃)₂;    -   R¹, R², R³, R⁴ and R⁵═H and R═Si_(x)H_(2x+1) (x=1 to 4);    -   the precursor being SiH₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si₂H₅N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si₃H₇N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si₄H₉N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   R¹, R², R³, R⁴ and R⁵═H and R═C_(y)H_(2y+1) (y=1 to 6);    -   the precursor being (Me)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (Et)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (nPr)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (iPr)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (Bu)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (iBu)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (tBu)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (amyl)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (hexyl)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiMe₃)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiEt₃)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si(iPr)₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si(nPr)₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si(Bu)₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si(iBu)₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si(tBu)₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si(amyl)₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being Si(hexyl)₃N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiHMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiHEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(iPr)₂N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(nPr)₂N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(Bu)₂N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(iBu)₂N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(tBu)₂N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(amyl)₂N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(hexyl)₂N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH2Me₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH2Et₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(iPr)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(nPr)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(Bu)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(iBu)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(tBu)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(amyl)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH₂(hexyl)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₃—CH₂—SiH₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiMe₃-CH₂—SiMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiMe₃-CH₂—CH₂—SiMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiEt₃-CH₂—SiEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiEt₃-CH₂—CH₂—SiEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NiPr₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NnPr₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂NMeEt)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂Piperidine)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂Pyrolidine)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂Pyrolle)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂Imidazole)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH₂Pyrimidine)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being (SiH(NMe₂)₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   the precursor being SiH(NEt₂)₂)N(SiH₂—CH₂—CH₂—SiH₃)₂;    -   R¹, R², R³ and R⁴═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1),        wherein u=1-6 and v=1-4;    -   R², R³, R⁴ and R⁵═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1),        wherein u=1-6 and v=1-4;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NH₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NMe₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NMeEt))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NEt₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NnPr₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NiPr₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NBu₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NiBu₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NtBu₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NAm₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NCyPentyl₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(Nhexyl₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NCyHex₂))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NMeH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NEtH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NnPrH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NiPrH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NBuH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NiBuH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NtBuH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(NAmH))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(pyridine))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(pyrrole))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(pyrrolidine))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(imidazole))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(piperidine))₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH₂(pyrimidine))₂;    -   R¹, R² and R³═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1), wherein        u=1-6 and v=1-4;    -   R², R³ and R⁴═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1), wherein        u=1-6 and v=1-4;    -   the precursor being RN(SiH(CH₂═CH)—CH₂—CH₂—SiH₂(CH₂═CH))₂;    -   the precursor being        RN(SiH(CH₂═CH—CH₂)—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₂;    -   the precursor being RN(SiH(NH₂)—CH₂—CH₂—SiH₂(NH₂))₂;    -   the precursor being RN(SiH(NMe₂)-CH₂—CH₂—SiH₂(NMe₂))₂;    -   the precursor being RN(SiH(NMeEt)-CH₂—CH₂—SiH₂(NMeEt))₂;    -   the precursor being RN(SiH(NEt₂)-CH₂—CH₂—SiH₂(NEt₂))₂;    -   the precursor being RN(SiH(NnPr₂)-CH₂—CH₂—SiH₂(NnPr₂))₂;    -   the precursor being RN(SiH(NiPr₂)-CH₂—CH₂—SiH₂(NiPr₂))₂;    -   the precursor being RN(SiH(NBu₂)-CH₂—CH₂—SiH₂(NBu₂))₂;    -   the precursor being RN(SiH(NiBu₂)-CH₂—CH₂—SiH₂(NiBu₂))₂;    -   the precursor being RN(SiH(NtBu₂)-CH₂—CH₂—SiH₂(NtBu₂))₂;    -   the precursor being RN(SiH(NAm₂)-CH₂—CH₂—SiH₂(NAm₂))₂;    -   the precursor being        RN(SiH(NCyPentyl₂)-CH₂—CH₂—SiH₂(NCyPentyl₂))₂;    -   the precursor being RN(SiH(Nhexyl₂)-CH₂—CH₂—SiH₂(Nhexyl₂))₂;    -   the precursor being RN(SiH(NCyHex₂)-CH₂—CH₂—SiH₂(NCyHex₂))₂;    -   the precursor being RN(SiH(NMeH)—CH₂—CH₂—SiH₂(NMeH))₂;    -   the precursor being RN(SiH(NEtH)—CH₂—CH₂—SiH₂(NEtH))₂;    -   the precursor being RN(SiH(NnPrH)—CH₂—CH₂—SiH₂(NnPrH))₂;    -   the precursor being RN(SiH(NiPrH)—CH₂—CH₂—SiH₂(NiPrH))₂;    -   the precursor being RN(SiH(NBuH)—CH₂—CH₂—SiH₂(NBuH))₂;    -   the precursor being RN(SiH(NiBuH)—CH₂—CH₂—SiH₂(NiBuH))₂;    -   the precursor being RN(SiH(NtBuH)—CH₂—CH₂—SiH₂(NtBuH))₂;    -   the precursor being RN(SiH(NAmH)—CH₂—CH₂—SiH₂(NAmH))₂;    -   the precursor being RN(SiH(pyridine)-CH₂—CH₂—SiH₂(pyridine))₂;    -   the precursor being RN(SiH(pyrrole)-CH₂—CH₂—SiH₂(pyrrole))₂;    -   the precursor being        RN(SiH(pyrrolidine)-CH₂—CH₂—SiH₂(pyrrolidine))₂;    -   the precursor being RN(SiH(imidazole)-CH₂—CH₂—SiH₂(imidazole))₂;    -   the precursor being        RN(SiH(piperidine)-CH₂—CH₂—SiH₂(piperidine))₂;    -   the precursor being        RN(SiH(pyrimidine)-CH₂—CH₂—SiH₂(pyrimidine))₂;    -   R³, R⁴ and R⁵═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1), wherein        u=1-6 and v=1-4;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(CH₂═CH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NH₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NMe₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NMeEt)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NEt₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NnPr₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NiPr₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NBu₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NiBu₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NtBu₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NAm₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NCyPentyl₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(Nhexyl₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NCyHex₂)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NMeH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NEtH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NnPrH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NiPrH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NBuH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NiBuH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NtBuH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(NAmH)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(pyridiHNe)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(pyrrole)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(pyrrolidiHNe)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(imidazole)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(piperidine)₂)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—SiH(pyrimidine)₂)₂; R⁴ and        R⁵═H and R═H, C_(u)H_(2u+1), or SivH_(2v-1), wherein u=1-6 and        v=1-4;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si—(CH₂═CH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NH₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NMe₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NMeEt)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NEt₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NnPr₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NiPr₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NBu₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NiBu₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NtBu₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NAm₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NCyPentyl₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(Nhexyl₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NCyHex₂)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NMeH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NEtH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NnPrH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NiPrH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NBuH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NiBuH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NtBuH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(NAmH)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(pyridine)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(pyrrole)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(pyrrolidine)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(imidazole)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(piperidine)₃)₂;    -   the precursor being RN(SiH₂—CH₂—CH₂—Si(pyrimidine)₃)₂;    -   at least one of R², R³, R⁴, and R⁵ being H;    -   R², R³, R⁴, and R⁵ all being H;    -   at least one of R², R³, R⁴, and R⁵ being a vinyl group;    -   R being H;    -   t=1;    -   the precursor being [—NR—R⁴R⁵Si—CH₂—SiR²R³—]_(n);    -   at least one of R, R², R³, R⁴, or R⁵ being vinyl;    -   at least one of R, R², R³, R⁴, or R⁵ being allyl;    -   at least one of R, R², R³, R⁴, or R⁵ being phenyl;    -   the precursor comprising [—NR—R⁴R⁵Si—(CH₂)—SiR²R³—]_(n) units        and a [—NR—R⁴R⁵Si—(CH₂)—SiR¹R²R³] end-cap;    -   the precursor comprising [—NR—R⁴R⁵Si—(CH₂)—SiR²R³—]_(n) units        and a [—NR—R⁴R⁵Si—(CH₂)—SiR²R³—NR¹R²] end-cap;    -   R, R², R³, R⁴ and R⁵═H;    -   the precursor being [—NH—SiH₂—CH₂—SiH₂—]_(n);    -   —R═Si_(x)H_(2x+1) (x=1 to 4) and R², R³, R⁴ and R⁵═H;    -   the precursor being [—N(SiH₃)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si₂H₅)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si₃H₇)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si₄H₉)—SiH₂—CH₂—SiH₂—]_(n);    -   R═C_(y)H_(2y+1) (y=1 to 6) and R², R³, R⁴ and R⁵═H;    -   the precursor being [—N(CH₃)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₂H₅)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₃H₇)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₄H₉)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₅H₁₁)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₆H₁₃)—SiH₂—CH₂—SiH₂—]_(n);    -   R², R³, R⁴ and R⁵═H and        R═R^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) wherein b=1 to 2        and R^(1′), R^(2′), R^(3′), R^(4′) and R^(5′)═H or a C₁-C₆        hydrocarbon;    -   the precursor being [—N(SiH₃—CH₂—SiH₂)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₃—CH₂—CH₂—SiH₂)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiMe₃-CH₂—SiMe₂)—SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being        [—N(SiMe₃-CH₂—CH₂—SiMe₂)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiEt₃-CH₂—SiEt₂)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being        [—N(SiEt₃-CH₂—CH₂—SiEt₂)-SiH₂—CH₂—SiH₂—]_(n);    -   R², R³, R⁴ and R⁵═H;    -   the precursor being [—N(SiMe₃)-H₂Si—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiEt₃)-H₂Si—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(iPr)₃-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(nPr)₃-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(Bu)₃-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(iBu)₃-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(tBu)₃-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(amyl)₃-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(hexyl)₃-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—Nx(SiH(Me)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(Et)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(iPr)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(nPr)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(Bu)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(iBu)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(tBu)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(amyl)₂-SiH₂-CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(hexyl)₂-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(Me)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(Et)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(iPr)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(nPr)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(Bu)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(iBu)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(tBu)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(amyl)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(hexyl)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NMe₂)-H₂Si—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NEt₂)-H₂Si—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NiPr₂)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NnPr₂)-SiH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NMeEt)-H₂Si—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(NMe₂)₂)-H₂Si—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(NEt₂)₂)-H₂Si—CH₂—SiH₂—]_(n);    -   R, R³, R⁴ and R⁵═H;    -   the precursor being [—NH—H₂Si—CH₂—SiH(CH₂═CH₂)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NH₂)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NMe₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NMeEt)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NEt₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NnPr₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NiPr₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NBu₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NiBu₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NtBu₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NAm₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NCyPentyl₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(Nhexyl₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NCyHex₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NMeH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NEtH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NnPrH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NiPrH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NBuH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NiBuH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NtBuH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(NAmH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(pyridine)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(pyrrole)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(pyrrolidine)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(imidazole)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(piperidine)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—SiH(pyrimidine)-]_(n);    -   R, R⁴ and R⁵═H;    -   the precursor being [—NH—H₂Si—CH₂—Si—(CH₂═CH₂)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si—(CH₂—CH₂═CH₂)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NH₂)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NMe₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NMeEt)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NEt₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NnPr₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NiPr₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NBu₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NiBu₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NtBu₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NAm₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NCyPentyl₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(Si(Nhexyl₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NCyHex₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NMeH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NEtH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NnPrH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NiPrH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NBuH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NiBuH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NtBuH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(NAmH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(pyridine)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(pyrrole)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(pyrrolidine)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(imidazole)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(piperidine)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—Si(pyrimidine)₂-]_(n);    -   R, R³ and R⁵═H;    -   the precursor being [—NH—SiH(CH₂═CH₂)—CH₂—SiH(CH₂═CH₂)—]_(n);    -   the precursor being        [—NH—SiH(CH₂—CH₂═CH₂)—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n);    -   the precursor being [—NH—SiH(NH₂)—CH₂—SiH(NH₂)—]_(n);    -   the precursor being [—NH—SiH(NMe₂)-CH₂—SiH(NMe₂)-]_(n);    -   the precursor being [—NH—SiH(NMeEt)-CH₂—SiH(NMeEt)-]_(n);    -   the precursor being [—NH—SiH(NEt₂)-CH₂—SiH(NEt₂)-]_(n);    -   the precursor being [—NH—SiH(NnPr₂)-CH₂—SiH(NnPr₂)-]_(n);    -   the precursor being [—NH—SiH(NiPr₂)-CH₂—SiH(NiPr₂)-]_(n);    -   the precursor being [—NH—SiH(NBu₂)-CH₂——SiH(NBu₂)-]_(n);    -   the precursor being [—NH—SiH(NiBu₂)-CH₂—SiH(NiBu₂)-]_(n);    -   the precursor being [—NH—SiH(NtBu₂)-CH₂—SiH(NtBu₂)-]_(n);    -   the precursor being [—NH—SiH(NAm₂)-CH₂—SiH(NAm₂)-]_(n);    -   the precursor being        [—NH—SiH(NCyPentyl₂)-CH₂—SiH(NCyPentyl₂)-]_(n);    -   the precursor being [—NH—SiH(Nhexyl₂)-CH₂—SiH(Nhexyl₂)-]_(n);    -   the precursor being [—NH—SiH(NCyHex₂)-CH₂—SiH(NCyHex₂)-]_(n);    -   the precursor being [—NH—SiH(NMeH)—CH₂—SiH(NMeH)—]_(n);    -   the precursor being [—NH—SiH(NEtH)—CH₂—SiH(NEtH)—]_(n);    -   the precursor being [—NH—SiH(NnPrH)—CH₂—SiH(NnPrH)—]_(n);    -   the precursor being [—NH—SiH(NiPrH)—CH₂—SiH(NiPrH)—]_(n);    -   the precursor being [—NH—SiH(NBuH)—CH₂—SiH(NBuH)—]_(n);    -   the precursor being [—NH—SiH(NiBuH)—CH₂—SiH(NiBuH)—]_(n);    -   the precursor being [—NH—SiH(NtBuH)—CH₂—SiH(NtBuH)—]_(n);    -   the precursor being [—NH—SiH(NAmH)—CH₂—SiH(NAmH)—]_(n);    -   the precursor being [—NH—SiH(pyridine)-CH₂—SiH(pyridine)-]_(n);    -   the precursor being [—NH—SiH(pyrrole)-CH₂—SiH(pyrrole)-]_(n);    -   the precursor being        [—NH—SiH(pyrrolidine)-CH₂—SiH(pyrrolidine)-]_(n);    -   the precursor being        [—NH—SiH(imidazole)-CH₂—SiH(imidazole)-]_(n);    -   the precursor being        [—NH—SiH(piperidine)-CH₂—SiH(piperidine)-]_(n);    -   the precursor being        [—NH—SiH(pyrimidine)-CH₂—SiH(pyrimidine)-]_(n);    -   t=2;    -   the precursor being [—NR—R⁴R⁵Si—(CH₂)₂—SiR²R³—]_(n);    -   the precursor comprising [—NR—R⁴R⁵Si—(CH₂)₂—SiR²R³—]_(n) units        and a [—NR—R⁴R⁵Si—(CH₂)₂—SiR¹R²R³—] end-cap;    -   the precursor comprising [—NR—R⁴R⁵Si—(CH₂)₂—SiR²R³—]_(n) units        and a [—NR—R⁴R⁵Si—(CH₂)₂—SiR²R³—NR¹R²] end-cap;    -   R, R², R³, R⁴ and R⁵═H;    -   the precursor being [—NH—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   R═Si_(x)H_(2x+1) (x=1 to 4) and R², R³, R⁴ and R⁵═H;    -   the precursor being [—N(SiH₃)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si₂H₅)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si₃H₇)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si₄H₉)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   R═C_(y)H_(2y+1) (y=1 to 6) and R², R³, R⁴ and R⁵═H;    -   the precursor being [—N(CH₃)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₂H₅)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₃H₇)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₄H₉)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₅H₁₁)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(C₆H₁₃)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   R², R³, R⁴ and R⁵═H;    -   the precursor being [—N(SiMe₃)-H₂Si—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiEt₃)-H₂Si—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(iPr)₃-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(nPr)₃-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(Bu)₃-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(iBu)₃-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(tBu)₃-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(amyl)₃-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(Si(hexyl)₃-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—Nx(SiH(Me)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(Et)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(iPr)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(nPr)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(Bu)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(iBu)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(tBu)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(amyl)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(hexyl)₂-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(Me)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(Et)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(iPr)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(nPr)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(Bu)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(iBu)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(tBu)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(amyl)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂(hexyl)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NMe₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NEt₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NiPr₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NnPr₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH₂NMeEt)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(NMe₂)₂)-SiH₂——CH₂—CH₂—SiH₂—]_(n);    -   the precursor being [—N(SiH(NEt₂)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   R², R³, R⁴ and R⁵═H and        R═R^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) wherein b=1 to 2        and R^(1′), R^(2′), R^(3′), R^(4′) and R^(5′)═H or C₁-C₆        hydrocarbon;    -   the precursor being [—N(SiH₃—CH₂—SiH₂)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being        [—N(SiH₃—CH₂—CH₂—SiH₂)—SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being        [—N(SiMe₃-CH₂—SiMe₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being        [—N(SiMe₃-CH₂—CH₂—SiMe₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being        [—N(SiEt₃-CH₂—SiEt₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   the precursor being        [—N(SiEt₃-CH₂—CH₂—SiEt₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n);    -   R, R³, R⁴ and R⁵═H;    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(CH₂═CH₂)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NH₂)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NMe₂)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NMeEt)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NEt₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NnPr₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NiPr₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NBu₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NiBu₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NtBu₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NAm₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NCyPentyl₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(Nhexyl₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NCyHex₂)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NMeH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NEtH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NnPrH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NiPrH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NBuH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NiBuH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NtBuH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(NAmH)—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(pyridine)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(pyrrole)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(pyrrolidine)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(imidazole)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(piperidine)-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—SiH(pyrimidine)-]_(n);    -   R, R⁴ and R⁵═H;    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si—(CH₂═CH₂)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si—(CH₂—CH₂═CH₂)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NH₂)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NMe₂)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NMeEt)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NEt₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NnPr₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NiPr₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NBu₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NiBu₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NtBu₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NAm₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NCyPentyl₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(Si(Nhexyl₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NCyHex₂)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NMeH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NEtH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NnPrH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NiPrH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NBuH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NiBuH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NtBuH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(NAmH)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(pyridine)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(pyrrole)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(pyrrolidine)₂-]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(imidazole)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(piperidine)₂—]_(n);    -   the precursor being [—NH—H₂Si—CH₂—CH₂—Si(pyrimidine)₂—]_(n);    -   R, R³ and R⁵═H;    -   the precursor being        [—NH—SiH(CH₂═CH₂)—CH₂—CH₂—SiH(CH₂═CH₂)—]_(n);    -   the precursor being        [—NH—SiH(CH₂—CH₂═CH₂)—CH₂—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n);    -   the precursor being [—NH—SiH(NH₂)—CH₂—CH₂—SiH(NH₂)—]_(n);    -   the precursor being [—NH—SiH(NMe₂)-CH₂—CH₂—SiH(NMe₂)-]_(n);    -   the precursor being [—NH—SiH(NMeEt)-CH₂—CH₂—SiH(NMeEt)-]_(n);    -   the precursor being [—NH—SiH(NEt₂)-CH₂—CH₂—SiH(NEt₂)-]_(n);    -   the precursor being [—NH—SiH(NnPr₂)-CH₂—CH₂—SiH(NnPr₂)-]_(n);    -   the precursor being [—NH—SiH(NiPr₂)-CH₂—CH₂—SiH(NiPr₂)-]_(n);    -   the precursor being [—NH—SiH(NBu₂)-CH₂—CH₂—SiH(NBu₂)-]_(n);    -   the precursor being [—NH—SiH(NiBu₂)-CH₂—CH₂—SiH(NiBu₂)-]_(n);    -   the precursor being [—NH—SiH(NtBu₂)-CH₂—CH₂—SiH(NtBu₂)-]_(n);    -   the precursor being [—NH—SiH(NAm₂)-CH₂—CH₂—SiH(NAm₂)-]_(n);    -   the precursor being        [—NH—SiH(NCyPentyl₂)-CH₂CH₂—SiH(NCyPentyl₂)-]_(n);    -   the precursor being        [—NH—SiH(Nhexyl₂)-CH₂—CH₂—SiH(Nhexyl₂)-]_(n);    -   the precursor being        [—NH—SiH(NCyHex₂)-CH₂—CH₂—SiH(NCyHex₂)-]_(n);    -   the precursor being [—NH—SiH(NMeH)—CH₂—CH₂—SiH(NMeH)—]_(n);    -   the precursor being [—NH—SiH(NEtH)—CH₂—CH₂—SiH(NEtH)—]_(n);    -   the precursor being [—NH—SiH(NnPrH)—CH₂—CH₂—SiH(NnPrH)—]_(n);    -   the precursor being [—NH—SiH(NiPrH)—CH₂—CH₂—SiH(NiPrH)—]_(n);    -   the precursor being [—NH—SiH(NBuH)—CH₂—CH₂—SiH(NBuH)—]_(n);    -   the precursor being [—NH—SiH(NiBuH)—CH₂—CH₂—SiH(NiBuH)—]_(n);    -   the precursor being [—NH—SiH(NtBuH)—CH₂—CH₂—SiH(NtBuH)—]_(n);    -   the precursor being [—NH—SiH(NAmH)—CH₂—CH₂—SiH(NAmH)—]_(n);    -   the precursor being        [—NH—SiH(pyridine)-CH₂—CH₂—SiH(pyridine)-]_(n);    -   the precursor being        [—NH—SiH(pyrrole)-CH₂—CH₂—SiH(pyrrole)-]_(n);    -   the precursor being        [—NH—SiH(pyrrolidine)-CH₂—CH₂—SiH(pyrrolidine)-]_(n);    -   the precursor being        [—NH—SiH(imidazole)-CH₂—CH₂—SiH(imidazole)-]_(n);    -   the precursor being        [—NH—SiH(piperidine)-CH₂—CH₂—SiH(piperidine)-]_(n);    -   the precursor being        [—NH—SiH(pyrimidine)-CH₂—CH₂—SiH(pyrimidine)-]_(n);    -   the Si-containing film forming composition comprising between        approximately 0.1 molar % and approximately 50 molar % of the        precursor;    -   the Si-containing film forming composition comprising between        approximately 93% w/w to approximately 100% w/w of the        precursor;    -   the Si-containing film forming composition comprising between        approximately 99% w/w to approximately 100% w/w of the        precursor;    -   the Si-containing film forming composition comprising between        approximately 0 ppmw and 200 ppmw of Cl;    -   the Si-containing film forming composition comprising between        approximately 0 ppmw and 50 ppmw of Cl;    -   further comprising a solvent;    -   the solvent being selected from the group consisting of C₁-C₁₆        hydrocarbons, THF, DMO, ether, pyridine, ketones, esters, and        combinations thereof;    -   the solvent being a C₁-C₁₆ saturated or unsaturated hydrocarbon;    -   the solvent being tetrahydrofuran (THF);    -   the solvent being dimethyl oxalate (DMO);    -   the solvent being ether;    -   the solvent being pyridine;    -   the solvent being methyl isobutyl ketone;    -   the solvent being cyclohexanone;    -   the solvent being ethanol;    -   the solvent being isopropanol;    -   further comprising a catalyst or a radical generator;    -   the radical generator being a photoinitiator, such as a phenone,        a quinine, or a metallocene;    -   further comprising a thermal radical initiator, such as a        peroxide or an azo compound comprising an —N═N— unit; or    -   the Si-containing film forming composition comprising between        approximately 0 ppmw and 100 ppb of each metal selected from        alkaline metals, alkaline earth metals, Al, and transition        metals (as defined by the International Union of Pure and        Applied Chemistry (IUPAC)).

Also disclosed are methods of depositing a Si-containing layer on asubstrate. The vapor of any of the Si-containing film formingcompositions disclosed above, but preferably those of Formula (I), isintroduced into a reactor having a substrate disposed therein. At leastpart of the precursor is deposited onto the substrate to form aSi-containing layer using a vapor deposition method. The disclosedmethods may include one or more of the following aspects:

-   -   introducing into the reactor a vapor comprising a second        precursor;    -   the second precursor comprising an element selected from the        group consisting of group 2, group 13, group 14, transition        metal, lanthanides, and combinations thereof;    -   the element of the second precursor being selected from B, Zr,        Hf, Ti, Nb, V, Ta, Al, Si, Ge;    -   introducing a co-reactant into the reactor;    -   the co-reactant being selected from the group consisting of O₂,        O₃, H₂O, H₂O₂, NO, NO₂, a carboxylic acid, an alcohol,        ethanolamine, radicals thereof, and combinations thereof;    -   the co-reactant being plasma treated oxygen;    -   the co-reactant being ozone;    -   the Si-containing layer being a silicon oxide containing layer;    -   the co-reactant being selected from the group consisting of H₂,        NH₃, (SiH₃)₃N, hydridosilanes (such as SiH₄, Si₂H₆, Si₃H₈,        Si₄H₁₀, Si₅H₁₀, Si₆H₁₂), chlorosilanes and chloropolysilanes        (such as SiHCl₃, SiH₂Cl₂, SiH₃Cl, Si₂Cl₆, Si₂HCl₅, Si₃Cl₈),        alkysilanes (such as Me₂SiH₂, Et₂SiH₂, MeSiH₃, EtSiH₃),        hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe), organic amines        (such as NMeH₂, NEtH₂, NMe₂H, NEt₂H, NMe₃, NEt₃, (SiMe₃)₂NH),        diamines (such as ethylene diamine, dimethylethylene diamine,        tetramethylethylene diamine), pyrazoline, pyridine, B-containing        molecules (such as B₂H₆, trimethylboron, triethylboron,        borazine, substituted borazine, dialkylaminoboranes), alkyl        metals (such as trimethylaluminum, triethylaluminum,        dimethylzinc, diethylzinc), radical species thereof, and        mixtures thereof.    -   the co-reactant being selected from the group consisting of H₂,        NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂, N(SiH₃)₃, hydrogen        radicals thereof, and mixtures thereof;    -   the co-reactant being HCDS or PCDS;    -   the co-reactant being a saturated or unsaturated, linear,        branched or cyclic hydrocarbon;    -   the co-reactant being ethylene;    -   the co-reactant being acetylene;    -   the co-reactant being propylene;    -   the co-reactant being isoprene;    -   the co-reactant being cyclohexane;    -   the co-reactant being cyclohexene;    -   the co-reactant being cyclohexadiene;    -   the co-reactant being pentene;    -   the co-reactant being pentyne;    -   the co-reactant being cyclopentane;    -   the co-reactant being butadiene;    -   the co-reactant being cyclobutane;    -   the co-reactant being terpinene;    -   the co-reactant being octane;    -   the co-reactant being octene;    -   the vapor deposition process being a chemical vapor deposition        process;    -   the vapor deposition process being an atomic layer deposition        (ALD) process;    -   the vapor deposition process being a spatial ALD process;    -   the vapor deposition process being a flowable chemical vapor        deposition process (F-CVD);    -   the silicon-containing layer being SiO₂;    -   the silicon-containing layer being SiC;    -   the silicon-containing layer being SiN;    -   the silicon-containing layer being SiON;    -   the silicon-containing layer being SiOC;    -   the silicon-containing layer being SiONC;    -   the silicon-containing layer being SiBN;    -   the silicon-containing layer being SiBCN;    -   the silicon-containing layer being SiCN;    -   the silicon-containing layer being SiMCO, in which M is selected        from Zr, Hf, Ti, Nb, V, Ta, Al, Ge; or    -   further comprising annealing the Si-containing layer.

Methods of forming Si-containing films on substrates are also disclosedusing the disclosed precursors. Any of the Si-containing film formingcompositions disclosed above, but preferably those of formula (II), iscontacted with the substrate and the Si-containing film formed via aspin coating, spray coating, dip coating, or slit coating technique toform the Si-containing film. The disclosed methods may include thefollowing aspects:

-   -   the Si-containing film forming composition further comprising a        solvent selected from the group consisting of C₅-C₁₆ branched,        linear, saturated or unsaturated hydrocarbons; THF; DMO; ether;        pyridine; ketones; esters; and combinations thereof;    -   the solvent being a C₅-C₁₆ saturated or insaturated hydrocarbon;    -   the solvent being ether;    -   the solvent being methyl isobutyl ketone;    -   the solvent being cyclohexanone;    -   the Si-containing film forming composition further comprising a        catalyst or a radical generator;    -   the radical generator being a photoinitiator;    -   the radical generator being a phenone;    -   the radical generator being a quinine;    -   the radical generator being a metallocene;    -   the radical generator being a thermal radical initiator;    -   the radical generator being a peroxide;    -   the radical generator being an azo compound comprising an —N═N—        unit;    -   the catalyst being a Lewis acid;    -   the catalyst being a photo-acid generator;    -   the catalyst being a hydrosilylation catalyst;    -   the Lewis acid being Tris(pentafluorophenyl)borane B(C₆F₅)₃;    -   the Lewis acid being a derivative;    -   the Lewis acid being a non-coordinating anion formed by the        complexation of B(C₆F₅)₃ with a metallocene compound;    -   forming the Si-containing film via a spin coating technique;    -   forming the Si-containing film via a spray coating technique;    -   forming the Si-containing film via a dip coating technique;    -   forming the Si-containing film via a slit coating technique;    -   annealing the Si-containing film;    -   UV-curing the Si containing film;    -   UV curing the Si containing film under a reactive atmosphere to        enhance the cross linking of the oligomers; or    -   laser treating the Si-containing film.

Notation and Nomenclature

The following detailed description and claims utilize a number ofabbreviations, symbols, and terms, which are generally well known in theart. While definitions are typically provided with the first instance ofeach acronym, for convenience, Table 1 provides a list of theabbreviations, symbols, and terms used along with their respectivedefinitions.

TABLE 1 a or an One or more than one Approximately ±10% of the valuestated or about LCD-TFT liquid-crystal display - thin-film transistorTFT thin-film transistor MIM Metal-insulator-metal DRAM dynamicrandom-access memory CVD chemical vapor deposition LPCVD low pressurechemical vapor deposition PCVD pulsed chemical vapor deposition SACVDsub-atmospheric chemical vapor deposition PECVD plasma enhanced chemicalvapor deposition APCVD atmospheric pressure chemical vapor depositionHWCVD hot-wire chemical vapor deposition f-CVD flowable chemical vapordeposition f-PECVD flowable plasma enhanced chemical vapor depositionMOCVD metal organic chemical vapor deposition ALD atomic layerdeposition spatial ALD spatial atomic layer deposition HWALD hot-wireatomic layer deposition PEALD plasma enhanced atomic layer depositionGCMS gas chromatography-mass spectrometry GPC Gel PermeationChromatography HCDS hexachlorodisilane (Si₂Cl₆) PCDS pentachlorodisilane(Si₂HCl₅) SRO Strontium Ruthenium Oxide LAH Lithium aluminium hydrideLiAlH₄ THF tetrahydrofuran Me Methyl Et Ethyl iPr iso-Propyl nPrn-propyl iBu iso-Butyl tBu tert-Butyl

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., Si refers to silicon, N refersto nitrogen, O refers to oxygen, C refers to carbon, etc.).

As used herein, the term “independently” when used in the context ofdescribing R groups should be understood to denote that the subject Rgroup is not only independently selected relative to other R groupsbearing the same or different subscripts or superscripts, but is alsoindependently selected relative to any additional species of that same Rgroup. For example in the formula MR¹ _(x) (NR²R³)_((4-x)), where x is 2or 3, the two or three R¹ groups may, but need not be identical to eachother or to R² or to R³. Further, it should be understood that unlessspecifically stated otherwise, values of R groups are independent ofeach other when used in different formulas.

As used herein, the term “hydrocarbon” refers to a saturated orunsaturated function group containing exclusively carbon and hydrogenatoms. As used herein, the term “alkyl group” refers to saturatedfunctional groups containing exclusively carbon and hydrogen atoms. Analkyl group is one type of hydrocarbon. Further, the term “alkyl group”refers to linear, branched, or cyclic alkyl groups. Examples of linearalkyl groups include without limitation, methyl groups, ethyl groups,propyl groups, butyl groups, etc. Examples of branched alkyls groupsinclude without limitation, t-butyl. Examples of cyclic alkyl groupsinclude without limitation, cyclopropyl groups, cyclopentyl groups,cyclohexyl groups, etc.

As used herein, the term “aryl” refers to aromatic ring compounds whereone hydrogen atom has been removed from the ring.

As used herein, the term “heterocyclic group” refers to a cycliccompound that has atoms of at least two different elements (notincluding H), such as C and S and/or N, as members of its ring.

As used herein, the term “carbosilazane” refers to a linear, branched,or cyclic molecule containing Si, C, and N atoms and at least one Si—Nbond;

As used herein, the acronym “DSP” stands for disilapropane, moreparticularly to H₃Si—CH₂—SiH₃ or its ligand analog —H₂Si—CH₂—SiH₃ or itsmonomer analog —H₂Si—CH₂—SiH₂—; the acronym “DSB” stands fordisilabutane, more particularly to H₃Si—CH₂—CH₂—SiH₃ or its ligandanalog —H₂Si—CH₂—CH₂—SiH₃ or its monomer analog —H₂Si—CH₂—CH₂—SiH₂—; andthe abbreviations “HNDSP2”, “RNDSP2”, “NDSP3”, “HNDSB2”, “RNDSB2”, and“NDSB3” stand for HN(DSP)₂, RN(DSP)₂, N(DSP)₃, HN(DSB)₂, RN(DSB)₂, andN(DSB)₃, respectively, wherein R is as defined.

As used herein, the abbreviation “Me” refers to a methyl group; theabbreviation “Et” refers to an ethyl group; the abbreviation “Pr” refersto any propyl group (i.e., n-propyl or isopropyl); the abbreviation“iPr” refers to an isopropyl group; the abbreviation “Bu” refers to anybutyl group (n-butyl, iso-butyl, t-butyl, sec-butyl); the abbreviation“tBu” refers to a tert-butyl group; the abbreviation “sBu” refers to asec-butyl group; the abbreviation “iBu” refers to an iso-butyl group;the abbreviation “Ph” refers to a phenyl group; the abbreviation “Am”refers to any amyl group (iso-amyl, sec-amyl, tert-amyl); theabbreviation “Cy” refers to a cyclic hydrocarbon group (cyclobutyl,cyclopentyl, cyclohexyl, etc.).

As used herein, the term “halogen-free” means X ranging from 0 ppmw to1000 ppmw, preferably from 0 ppmw to 500 ppmw, and more preferably from0 ppmw to 100 ppmw, wherein X═Cl, Br, or I).

The standard abbreviations of the elements from the periodic table ofelements are used herein. It should be understood that elements may bereferred to by these abbreviations (e.g., Si refers to silicon, N refersto nitrogen, O refers to oxygen, C refers to carbon, etc.).

Please note that the films or layers deposited, such as silicon oxide,are listed throughout the specification and claims without reference totheir proper stoichoimetry (i.e., SiO₂). The layers may include pure(Si) layers, silicide (M_(o)Si_(p)) layers, carbide (Si_(o)C_(p))layers, nitride (Si_(k)N_(l)) layers, oxide (Si₃O_(m)) layers, ormixtures thereof; wherein M is an element and k, l, m, n, o, and pinclusively range from 1 to 6. For instance, cobalt silicide isCo_(k)Si_(l), where k and I each range from 0.5 to 5. Similarly, anyreferenced layers may also include a Silicon oxide layer, Si_(n)O_(m),wherein n ranges from 0.5 to 1.5 and m ranges from 1.5 to 3.5. Morepreferably, the silicon oxide layer is SiO₂. The silicon oxide layer maybe a silicon oxide based dielectric material, such as organic based orsilicon oxide based low-k dielectric materials such as the Black DiamondII or III material by Applied Materials, Inc. Alternatively, anyreferenced silicon-containing layer may be pure silicon. Anysilicon-containing layers may also include dopants, such as B, C, P, Asand/or Ge.

Any and all ranges recited herein are inclusive of their endpoints(i.e., x=1 to 4 includes x=1, x=4, and x=any number in between),irrespective of whether the term “inclusively” is used.

BRIEF DESCRIPTION OF THE DRAWINGS

For a further understanding of the nature and objects of the presentinvention, reference should be made to the following detaileddescription, taken in conjunction with the accompanying drawings, inwhich like elements are given the same or analogous reference numbersand wherein:

FIG. 1 is a flow chart for an exemplary deposition process;

FIG. 2 is a GCMS chromatogram of the final product of the NDSP2 andNDSP3 mixture produced by the halogen-free synthesis route;

FIG. 3 is a GCMS chromatogram of the final product of the NDSP2 andNDSP3 mixture produced by the halogen-free synthesis route after the1^(st) fraction of Fractional distillation;

FIG. 4 is a GCMS chromatogram of the mixture of NDSP3 and HNDSP2produced by the halogen-free synthesis route after the 2^(nd) fractionof Fractional distillation;

FIG. 5 is a GCMS chromatogram of the colorless viscous oil after removalof HNDSP2 and NDSP3 produced by the halogen-free synthesis route;

FIGS. 6a and b are GCMS chromatogram of the final product of NDSP2selectively produced by the halogen involved synthesis route, taken withthe final product after 16 hours at room temperature (FIG. 6a ) andafter 8 weeks at room temperature (FIG. 6b ); and

FIG. 7 is a Gel Permation Chromatographic graph showing the molecularweight versus the polydispersity of the molecular weight distribution.

DESCRIPTION OF PREFERRED EMBODIMENTS

Disclosed are Si-containing film forming compositions comprisingcarbosilazane or polycarbosilazane (or polyorganosilazane) precursors.Also disclosed are methods of synthesizing the carbosilazane orpolycarbosilazane precursors and methods of using the same to depositsilicon-containing films for manufacturing semiconductors.

The disclosed precursors have the following formula:

R_(a)N(R⁴R⁵Si—(CH₂)_(m)SiR¹R²R³)_(3-a)   (I)

or a unit having the following formula:

[—NR—R⁴R⁵Si—(CH₂)_(t)—SiR²R³—]_(n)   (II)

wherein a=0 to 1; m=1 to 4; t=1 to 4; n=2 to 400;

-   R¹, R², R³, R⁴, and R⁵ are independently H, a hydrocarbon group (C₁    to C₆), or an alkylamino group having the formula NR″₂ and each R″    is independently H, a C₁-C₆ hydrocarbon group, a C₆-C₁₂ aryl, or    NR″₂ forms a cyclic amine group, and provided that at least one of    R¹, R², R³, R⁴, and R⁵ is H; and-   R is H; a C₁-C₆ hydrocarbon group; a silyl group having the formula    Si_(x)R′_(2x+1) with x=1 to 4 and each R′ independently ═H, a C₁-C₆    hydrocarbon group, or an alkylamino group having the formula NR″₂    and each R″ is independently H, a C₁-C₆ group, a C₆-C₁₂ aryl, or    NR″₂ forms a cyclic amine group; or a    R^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group, wherein b=1 to 2    and R^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) are independently H,    a C₁-C₆ hydrocarbon group, a C₆-C₁₂ aryl, or an alkylamino group    having the formula NR″₂ and each R″ is independently H, a C₁-C₆    group, a C₆-C₁₂ aryl, or NR″₂ forms a cyclic amine group; and    provided that at least one of R^(1′), R^(2′), R^(3′), R^(4′), and    R^(5′) is H. Preferably, m=1 to 2 and t=1 to 2. The R″ of the    alkylamino groups may be joined to form a cyclic chain on the N    atom. For example, NR″₂ may form pyridine, pyrrole, pyrrolidine, or    imidazole ring structures. The precursors may have improved    volatility when the precursor contains 6 Hs in formula (I) (i.e., R,    R¹, R², R³, R⁴ and R⁵ are each independently a H) or 5 Hs in each    N—Si—C—Si or N—Si—C—C—Si backbone unit in formula (II) (i.e., R, R²,    R³, R⁴ and R⁵ are each independently a H).

The disclosed precursors shown in formula (I) and (II) provideflexibilities to produce Si-containing film forming compositions thatspecifically have one element in more weight than the others dependingon applications. For example, if more Si is preferred in the film, R maybe a silane having the formula Si_(x)H_(2x+1) (x=1 to 4) or aR^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group wherein b=1 to 2. Ifmore N is preferred in the film, R, R¹, R², R³, R⁴, and R⁵ are eachindependently an alkylamino group having the formula NR″₂. If more C ispreferred in the film, R, R¹, R², R³, R⁴, and R⁵ may be a hydrocarbongroup (C1 to C12) or form a long carbon linking chain in the backboneunit, such as N—Si—C_(c)—Si (c=1 to 2).

The disclosed precursors contain no Si-halogen bonds which is importantbecause halogens may damage other layers in the substrate (e.g., low klayers, copper interconnect layers, etc.). The disclosed Si-containingfilm forming compositions are halogen-free and capable of formingglobally planarized, thermally stable and adherent dielectric layers andother dielectric-like layers or materials on semiconductor devices,semiconductor components, electronic components and layered materials.

The disclosed precursor may contain one or two hydrogen atoms directlybonded to the Si atom. The Si—H bonds of the disclosed precursors mayhelp to provide a larger growth rate per cycle in ALD processes whencompared to analogous Si-halogen containing precursors because the Hatoms occupy less surface area, resulting in more molecules on thesubstrate surface. Inclusion of the SiH bonds (i.e., hydridefunctionality) may produce less steric bulk, which may provide theprecursors with higher reactivity to the substrate than precursors thatdo not contain the SiH bond. These Si—H bonds may help increase thevolatility of the precursor, which is important for vapor depositionprocesses. As a result, for vapor depositions processes, at least one ofR¹, R², or R³ preferably ═H and at least one of R⁴ or R⁵ preferably ═Hin the disclosed precursors of Formula (I).

The disclosed precursor may contain one, two, or three amino groupsdirectly bonded to the Si atom. These Si—N bonds may help increasethermal stability of the precursor, which is also important for vapordeposition processes. The amino group may also help incorporate N and Catoms into the resulting film, which may make the resulting layer moreresistant to any subsequent etching processes.

One of ordinary skill in the art will recognize that the volatilityprovided by the Si—H bonds competes directly with the thermal stabilityprovided by the amino groups. Applicants believe that at leastHN(SiH(NiPr₂)-CH₂—SiH₃)₂ and HN(SiH₂—CH₂—SiH₂(NiPr₂))₂ successfullybalance those competing characteristics.

One of ordinary skill in the art will recognize that embodiments inwhich m=1 may produce precursors having higher volatility and lowermelting points, being more suitable for vapor deposition. Embodiments inwhich m=2 may also be suitable for vapor deposition when the resultingsilicon-containing film also contains carbon. Embodiments in which m=3or t=1-3 may be suitable for casting deposition methods, such as spin-onor dip coating.

Some of the disclosed Si-containing film forming compositions haveproperties suitable for vapor depositions methods, such as high vaporpressure, low melting point (preferably being in liquid form at roomtemperature), low sublimation point, and high thermal stability. TheSi-containing film forming compositions preferably are stable at atemperature producing a vapor pressure of 1-5 Torr. The carbosilazane orpolycarbosilazane (or polyorganosilazane) precursors in the disclosedSi-containing film forming compositions suitable for vapor depositiontypically have a molecular weight ranging from approximately 150 toapproximately 600, preferably from approximately 200 to approximately400.

Some of the disclosed Si-containing film forming compositions haveproperties suitable for spin coating, spray coating, dip coating, orslit coating methods, such as low vapor pressure, low melting point(preferably being in liquid form at room temperature), and goodsolubility in the conventional coating processes. The carbosilazane orpolycarbosilazane (or polyorganosilazane) precursors in the disclosedSi-containing film forming compositions suitable for these depositiontechniques typically have a molecular weight ranging from approximately500 to approximately 1,000,000, preferably from approximately 1,000 toapproximately 100,000, and more preferably from 3,000 to 50,000.

When a=0, the disclosed carbosilazane precursor presented in formula (I)has the following formula:

N(SiR⁴R⁵(CH₂)_(m)SiR¹R²R³)₃   (III).

When m=1, and R¹, R², R³, R⁴ and R⁵═H, the disclosed precursor presentedin formula (III) is tris(1,3-disilapropane)amine [N(SiH₂—CH₂—SiH₃)₃ orNDSP3]. As shown in the examples that follow, this liquid precursor issuitable for vapor deposition applications due at least partially to thebenefits discussed above for SiH bonds and low molecular weight.

Exemplary precursors presented in formula (III) wherein m=1, R¹, R², R³and R⁴═H include, but are not limited to, N(SiH(CH₂═CH)—CH₂—SiH₃)₃,N(SiH(CH₂═CH—CH₂)—CH₂—SiH₃)₃, N(SiH(NH₂)—CH₂—SiH₃)₃,N(SiH(NMe₂)-CH₂—SiH₃)₃, N(SiH(NMeEt)-CH₂—SiH₃)₃, N(SiH(NEt₂)-CH₂—SiH₃)₃,N(SiH(NnPr₂)-CH₂—SiH₃)₃, N(SiH(NiPr₂)-CH₂—SiH₃)₃,N(SiH(NBu₂)-CH₂—SiH₃)₃, N(SiH(NiBu₂)-CH₂—SiH₃)₃,N(SiH(NtBu₂)-CH₂—SiH₃)₃, N(SiH(NAm₂)-CH₂—SiH₃)₃,N(SiH(NCyPentyl₂)-CH₂—SiH₃)₃, N(SiH(Nhexyl₂)-CH₂—SiH₃)₃,N(SiH(NCyHex₂)-CH₂—SiH₃)₃, N(SiH(NMeH)—CH₂—SiH₃)₃,N(SiH(NEtH)—CH₂—SiH₃)₃, N(SiH(NnPrH)—CH₂—SiH₃)₃,N(SiH(NiPrH)—CH₂—SiH₃)₃, N(SiH(NBuH)—CH₂—SiH₃)₃,N(SiH(NiBuH)—CH₂—SiH₃)₃, N(SiH(NtBuH)—CH₂—SiH₃)₃,N(SiH(NAmH)—CH₂—SiH₃)₃, N(SiH(pyridine)-CH₂—SiH₃)₃,N(SiH(pyrrole)-CH₂—SiH₃)₃, N(SiH(pyrrolidine)-CH₂—SiH₃)₃, andN(SiH(imidazole)-CH₂—SiH₃)₃.

Exemplary precursors presented in formula (III) wherein m=1, R², R³, R⁴and R⁵═H include, but are not limited to, N(SiH₂—CH₂—SiH₂(CH₂═CH))₃,N(SiH₂—CH₂—SiH₂(CH₂═CH—CH₂))₃, N(SiH₂—CH₂—SiH₂(NH₂))₃,N(SiH₂—CH₂—SiH₂(NMe₂))₃, N(SiH₂—CH₂—SiH₂(NMeEt))₃,N(SiH₂—CH₂—SiH₂(NEt₂))₃, N(SiH₂—CH₂—SiH₂(NnPr₂))₃,N(SiH₂—CH₂—SiH₂(NiPr₂))₃, N(SiH₂—CH₂—SiH₂(NBu₂))₃,N(SiH₂—CH₂—SiH₂(NiBu₂))₃, N(SiH₂—CH₂—SiH₂(NtBu₂))₃,N(SiH₂—CH₂—SiH₂(NAm₂))₃, N(SiH₂—CH₂—SiH₂(NCyPentyl₂))₃,N(SiH₂—CH₂—SiH₂(Nhexyl₂))₃, N(SiH₂—CH₂—SiH₂(NCyHex₂))₃,N(SiH₂—CH₂—SiH₂(NMeH))₃, N(SiH₂—CH₂—SiH₂(NEtH))₃,N(SiH₂—CH₂—SiH₂(NnPrH))₃, N(SiH₂—CH₂—SiH₂(NiPrH))₃,N(SiH₂—CH₂—SiH₂(NBuH))₃, N(SiH₂—CH₂—SiH₂(NiBuH))₃,N(SiH₂—CH₂—SiH₂(NtBuH))₃, N(SiH₂—CH₂—SiH₂(NAmH))₃,N(SiH₂—CH₂—SiH₂(pyridine))₃, N(SiH₂—CH₂—SiH₂(pyrrole))₃,N(SiH₂—CH₂—SiH₂(pyrrolidine))₃, and N(SiH₂—CH₂—SiH₂(imidazole))₃. Theseprecursors are suitable for vapor deposition due at least partially tothe benefits discussed above for SiH bonds and low molecular weight. Theterminal amino ligand may also provide improved thermal stability, aswell as an additional N and/or C source for the resulting film.

Exemplary precursors presented in formula (III) wherein m=1, R¹, R² andR³═H include, but are not limited to, N(Si—(CH₂═CH)₂—CH₂—SiH₃)₃,N(Si—(CH₂═CH—CH₂)₂—CH₂—SiH₃)₃, N(Si(NH₂)₂—CH₂—SiH₃)₃,N(Si(NMe₂)₂-CH₂—SiH₃)₃, N(Si(NMeEt)₂-CH₂—SiH₃)₃, N(SiNEt₂-CH₂—SiH₃)₃,N(Si(NnPr₂)₂-CH₂—SiH₃)₃, N(Si(NiPr₂)₂-CH₂—SiH₃)₃,N(Si(NBu₂)₂-CH₂—SiH₃)₃, N(Si(NiBu₂)₂-CH₂—SiH₃)₃,N(Si(NtBu₂)₂-CH₂—SiH₃)₃, N(Si(NAm₂)₂-CH₂—SiH₃)₃,N(Si(NCyPentyl₂)₂-CH₂—SiH₃)₃, N(Si(Nhexyl₂)₂-CH₂—SiH₃)₃,N(Si(NCyHexyl₂)₂-CH₂—SiH₃)₃, N(Si(NMeH)₂—CH₂—SiH₃)₃,N(Si(NEtH)₂—CH₂—SiH₃)₃, N(Si(NnPrH)₂—CH₂—SiH₃)₃,N(Si(NiPrH)₂—CH₂—SiH₃)₃, N(Si(NBuH)₂—CH₂—SiH₃)₃,N(Si(NiBuH)₂—CH₂—SiH₃)₃, N(Si(NtBuH)₂—CH₂—SiH₃)₃,N(Si(NAmH)₂—CH₂—SiH₃)₃, N(Si(pyridine)₂-CH₂—SiH₃)₃,N(Si(pyrrole)₂-CH₂—SiH₃)₃, N(Si(pyrrolidine)₂-CH₂—SiH₃)₃, andN(Si(imidazole)₂-CH₂—SiH₃)₃.

Exemplary precursors presented in formula (III) wherein m=1, R², R³ andR⁴═H include, but are not limited to N(SiH(CH₂═CH)—CH₂—SiH₂(CH₂═CH))₃,N(SiH(CH₂═CH—CH₂)—CH₂—SiH₂(CH₂═CH—CH₂))₃, N(SiH(NH₂)—CH₂—SiH₂(NH₂))₃,N(SiH(NMe₂)-CH₂—SiH₂(NMe₂))₃, N(SiH(NMeEt)-CH₂—SiH₂(NMeEt))₃,N(SiH(NEt₂)-CH₂—SiH₂(NEt₂))₃, N(SiH(NnPr₂)-CH₂—SiH₂(NnPr₂))₃,N(SiH(NiPr₂)-CH₂—SiH₂(NiPr₂))₃, N(SiH(NBu₂)-CH₂—SiH₂(NBu₂))₃,N(SiH(NiBu₂)-CH₂—SiH₂(NiBu₂))₃, N(SiH(NtBu₂)-CH₂—SiH₂(NtBu₂))₃,N(SiH(NAm₂)-CH₂—SiH₂(NAm₂))₃, N(SiH(NCyPentyl₂)-CH₂—SiH₂(NCyPentyl₂))₃,N(SiH(Nhexyl₂)-CH₂—SiH₂(Nhexyl₂))₃,N(SiH(NCyHexyl₂)-CH₂—SiH₂(NCyHexyl₂))₃, N(SiH(NMeH)—CH₂—SiH₂(NMeH))₃,N(SiH(NEtH)—CH₂—SiH₂(NEtH))₃, N(SiH(NnPrH)—CH₂—SiH₂(NnPrH))₃,N(SiH(NiPrH)—CH₂—SiH₂(NiPrH))₃, N(SiH(NBuH)—CH₂—SiH₂(NBuH))₃,N(SiH(NiBuH)—CH₂—SiH₂(NiBuH))₃, N(SiH(NtBuH)—CH₂—SiH₂(NtBuH))₃,N(SiH(NAmH)—CH₂—SiH₂(NAmH))₃, N(SiH(pyridine)-CH₂—SiH₂(pyridine))₃,N(SiH(pyrrole)-CH₂—SiH₂(pyrrole))₃,N(SiH(pyrrolidine)-CH₂—SiH₂(pyrrolidine))₃, andN(SiH(imidazole)-CH₂—SiH₂(imidazole))₃.

Exemplary precursors presented in formula (III) wherein m=1, R³, R⁴ andR⁵═H include but are not limited to, N(SiH₂—CH₂—SiH(CH₂═CH)₂)₃,N(SiH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₃, N(SiH₂—CH₂—SiH(NH₂)₂)₃,N(SiH₂—CH₂—SiH(NMe₂)₂)₃, N(SiH₂—CH₂—SiH(NMeEt)₂)₃,N(SiH₂—CH₂—SiH(NEt₂)₂)₃, N(SiH₂—CH₂—SiH(NnPr₂)₂)₃,N(SiH₂—CH₂—SiH(NiPr₂)₂)₃, N(SiH₂—CH₂—SiH(NBu₂)₂)₃,N(SiH₂—CH₂—SiH(NiBu₂)₂)₃, N(SiH₂—CH₂—SiH(NtBu₂)₂)₃,N(SiH₂—CH₂—SiH(NAm₂)₂)₃, N(SiH₂—CH₂—SiH(NCyPentyl₂)₂)₃,N(SiH₂—CH₂—SiH(Nhexyl₂)₂)₃, N(SiH₂—CH₂—SiH(NCyHexyl₂)₂)₃,N(SiH₂—CH₂—SiH(NMeH)₂)₃, N(SiH₂—CH₂—SiH(NEtH)₂)₃,N(SiH₂—CH₂—SiH(NnPrH)₂)₃, N(SiH₂—CH₂—SiH(NiPrH)₂)₃,N(SiH₂—CH₂—SiH(NBuH)₂)₃, N(SiH₂—CH₂—SiH(NiBuH)₂)₃,N(SiH₂—CH₂—SiH(NtBuH)₂)₃, N(SiH₂—CH₂—SiH(NAmH)₂)₃,N(SiH₂—CH₂—SiH(pyridine)₂)₃, N(SiH₂—CH₂—SiH(pyrrole)₂)₃,N(SiH₂—CH₂—SiH(pyrrolidine)₂)₃, and N(SiH₂—CH₂—SiH(imidazole)₂)₃. Theseprecursors may be suitable for either vapor deposition or coatingapplications due at least partially to the benefits discussed above forSiH bonds The terminal amino ligands may also provide improved thermalstability, as well as an additional N and/or C source for the resultingfilm. Finally, the listed precursors having lower molecular weights andhigher vapor pressures are better suited for vapor depositiontechniques, whereas those having higher molecular weights are bettersuited for coating techniques.

Exemplary precursors presented in formula (III) wherein m=1, R⁴ and R⁵═Hinclude, but are not limited to, N(SiH₂—CH₂—Si—(CH₂═CH)₃)₃,N(SiH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₃, N(SiH₂—CH₂—Si(NH₂)₃)₃,N(SiH₂—CH₂—Si(NMe₂)₃)₃, N(SiH₂—CH₂—Si(NMeEt)₃)₃, N(SiH₂—CH₂—Si(NEt₂)₃)₃,N(SiH₂—CH₂—Si(NnPr₂)₃)₃, N(SiH₂—CH₂—Si(NiPr₂)₃)₃,N(SiH₂—CH₂—Si(NBu₂)₃)₃, N(SiH₂—CH₂—Si(NiBu₂)₃)₃,N(SiH₂—CH₂—Si(NtBu₂)₃)₃, N(SiH₂—CH₂—Si(NAm₂)₃)₃,N(SiH₂—CH₂—Si(NCyPentyl₂)₃)₃, N(SiH₂—CH₂—Si(Nhexyl₂)₃)₃,N(SiH₂—CH₂—Si(NCyHexyl₂)₃)₃, N(SiH₂—CH₂—Si(NMeH)₃)₃,N(SiH₂—CH₂—Si(NEtH)₃)₃, N(SiH₂—CH₂—Si(NnPrH)₃)₃,N(SiH₂—CH₂—Si(NiPrH)₃)₃, N(SiH₂—CH₂—Si(NBuH)₃)₃,N(SiH₂—CH₂—Si(NiBuH)₃)₃, N(SiH₂—CH₂—Si(NtBuH)₃)₃,N(SiH₂—CH₂—Si(NAmH)₃)₃, N(SiH₂—CH₂—Si(pyridine)₃)₃,N(SiH₂—CH₂—Si(pyrrole)₃)₃, N(SiH₂—CH₂—Si(pyrrolidine)₃)₃, andN(SiH₂—CH₂—Si(imidazole)₃)₃. These precursors may be suitable for vapordeposition or coating applications due at least partially to thebenefits discussed above for SiH bonds The terminal amino ligands mayalso provide improved thermal stability, as well as an additional Nand/or C source for the resulting film. Finally, the listed precursorshaving lower molecular weights and higher vapor pressures are bettersuited for vapor deposition techniques, whereas those having highermolecular weights are better suited for coating techniques.

When m=2, R1, R², R³, R⁴ and R⁵═H, the disclosed carbosilazane precursoris tris(1,4-disilabutane)amine [N(SiH₂—CH₂—CH₂—SiH₃)₃ or NDSB3]. Thisliquid precursor is suitable for vapor deposition due at least partiallyto the benefits discussed above for SiH bonds and low molecular weight.

Exemplary precursors presented in formula (III) wherein m=2, R¹, R², R³and R⁴═H include, but are not limited to, N(SiH(CH₂═CH)—CH₂—CH₂—SiH₃)₃,N(SiH(CH₂═CH—CH₂)—CH₂—CH₂—SiH₃)₃, N(SiH(NH₂)—CH₂—CH₂—SiH₃)₃,N(SiH(NMe₂)-CH₂—CH₂—SiH₃)₃, N(SiH(NMeEt)-CH₂—CH₂—SiH₃)₃,N(SiH(NEt₂)-CH₂—CH₂—SiH₃)₃, N(SiH(NnPr₂)-CH₂—CH₂—SiH₃)₃,N(SiH(NiPr₂)-CH₂—CH₂—SiH₃)₃, N(SiH(NBu₂)-CH₂—CH₂—SiH₃)₃,N(SiH(NiBu₂)-CH₂—CH₂—SiH₃)₃, N(SiH(NtBu₂)-CH₂—CH₂—SiH₃)₃,N(SiH(NAm₂)-CH₂—CH₂—SiH₃)₃, N(SiH(NCyPentyl₂)-CH₂—CH₂—SiH₃)₃,N(SiH(Nhexyl₂)-CH₂—CH₂—SiH₃)₃, N(SiH(NCyHexyl₂)-CH₂—CH₂—SiH₃)₃,N(SiH(NMeH)—CH₂—CH₂—SiH₃)₃, N(SiH(NEtH)—CH₂—CH₂—SiH₃)₃,N(SiH(NnPrH)—CH₂—CH₂—SiH₃)₃, N(SiH(NiPrH)—CH₂—CH₂—SiH₃)₃,N(SiH(NBuH)—CH₂—CH₂—SiH₃)₃, N(SiH(NiBuH)—CH₂—CH₂—SiH₃)₃,N(SiH(NtBuH)—CH₂—CH₂—SiH₃)₃, N(SiH(NAmH)—CH₂—CH₂—SiH₃)₃,N(SiH(pyridine)-CH₂—CH₂—SiH₃)₃, N(SiH(pyrrole)-CH₂—CH₂—SiH₃)₃,N(SiH(pyrrolidine)-CH₂—CH₂—SiH₃)₃, and N(SiH(imidazole)-CH₂—CH₂—SiH₃)₃.

Exemplary precursors presented in formula (III) wherein m=2, R², R³, R⁴and R⁵═H include, but are not limited to, N(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH))₃,N(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₃, N(SiH₂—CH₂—CH₂—SiH₂(NH₂))₃,N(SiH₂—CH₂—CH₂—SiH₂(NMe₂))₃, N(SiH₂—CH₂—CH₂—SiH₂(NMeEt))₃,N(SiH₂—CH₂—CH₂—SiH₂(NEt₂))₃, N(SiH₂—CH₂—CH₂—SiH₂(NnPr₂))₃,N(SiH₂—CH₂—CH₂—SiH₂(NiPr₂))₃, N(SiH₂—CH₂—CH₂—SiH₂(NBu₂))₃,N(SiH₂—CH₂—CH₂—SiH₂(NiBu₂))₃, N(SiH₂—CH₂—CH₂—SiH₂(NtBu₂))₃,N(SiH₂—CH₂—CH₂—SiH₂(NAm₂))₃, N(SiH₂—CH₂—CH₂—SiH₂(NCyPentyl₂))₃,N(SiH₂—CH₂—CH₂—SiH₂(Nhexyl₂))₃, N(SiH₂—CH₂—CH₂—SiH₂(NCyHexyl₂))₃,N(SiH₂—CH₂—CH₂—SiH₂(NMeH))₃, N(SiH₂—CH₂—CH₂—SiH₂(NEtH))₃,N(SiH₂—CH₂—CH₂—SiH₂(NnPrH))₃, N(SiH₂—CH₂—CH₂—SiH₂(NiPrH))₃,N(SiH₂—CH₂—CH₂—SiH₂(NBuH))₃, N(SiH₂—CH₂—CH₂—SiH₂(NiBuH))₃,N(SiH₂—CH₂—CH₂—SiH₂(NtBuH))₃, N(SiH₂—CH₂—CH₂—SiH₂(NAmH))₃,N(SiH₂—CH₂—CH₂—SiH₂(pyridine))₃, N(SiH₂—CH₂—CH₂—SiH₂(pyrrole))₃,N(SiH₂—CH₂—CH₂—SiH₂(pyrrolidine))₃, andN(SiH₂—CH₂—CH₂—SiH₂(imidazole))₃. These precursors may be suitable forvapor deposition applications due at least partially to the benefitsdiscussed above for SiH bonds and low molecular weight. The terminalamino ligands may also provide improved thermal stability, as discussedabove, as well as an additional N and/or C source for the resultingfilm.

Exemplary precursors presented in formula (III) wherein m=2, R¹, R² andR³═H include, but are not limited to, N(Si—(CH₂═CH)₂—CH₂—CH₂—SiH₃)₃,N(Si—(CH₂═CH—CH₂)₂—CH₂—CH₂—SiH₃)₃, N(Si(NH₂)₂—CH₂—CH₂—SiH₃)₃,N(Si(NMe₂)₂-CH₂—CH₂—SiH₃)₃, N(Si(NMeEt)₂-CH₂—CH₂—SiH₃)₃,N(SiNEt₂-CH₂—CH₂—SiH₃)₃, N(Si(NnPr₂)₂-CH₂—CH₂—SiH₃)₃,N(Si(NiPr₂)₂-CH₂—CH₂—SiH₃)₃, N(Si(NBu₂)₂-CH₂—CH₂—SiH₃)₃,N(Si(NiBu₂)₂-CH₂—CH₂—SiH₃)₃, N(Si(NtBu₂)₂-CH₂—CH₂—SiH₃)₃,N(Si(NAm₂)₂-CH₂—CH₂—SiH₃)₃, N(Si(NCyPentyl₂)₂-CH₂—CH₂—SiH₃)₃,N(Si(Nhexyl₂)₂-CH₂—CH₂—SiH₃)₃, N(Si(NCyHexyl₂)₂-CH₂—CH₂—SiH₃)₃,N(Si(NMeH)₂—CH₂—CH₂—SiH₃)₃, N(Si(NEtH)₂—CH₂—CH₂—SiH₃)₃,N(Si(NnPrH)₂—CH₂—CH₂—SiH₃)₃, N(Si(NiPrH)₂—CH₂—CH₂—SiH₃)₃,N(Si(NBuH)₂—CH₂—CH₂—SiH₃)₃, N(Si(NiBuH)₂—CH₂—CH₂—SiH₃)₃,N(Si(NtBuH)₂—CH₂—CH₂—SiH₃)₃, N(Si(NAmH)₂—CH₂—CH₂—SiH₃)₃,N(Si(pyridine)₂-CH₂—CH₂—SiH₃)₃, N(Si(pyrrole)₂-CH₂—CH₂—SiH₃)₃,N(Si(pyrrolidine)₂-CH₂—CH₂—SiH₃)₃, and N(Si(imidazole)₂-CH₂—CH₂—SiH₃)₃.

Exemplary precursors presented in formula (III) wherein m=2, R², R³ andR⁴═H include, but are not limited to,N(SiH(CH₂═CH)—CH₂—CH₂—SiH₂(CH₂═CH))₃,N(SiH(CH₂═CH—CH₂)—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₃,N(SiH(NH₂)—CH₂—CH₂—SiH₂(NH₂))₃, N(SiH(NMe₂)-CH₂—CH₂—SiH₂(NMe₂))₃,N(SiH(NMeEt)-CH₂—CH₂—SiH₂(NMeEt))₃, N(SiH(NEt₂)-CH₂—CH₂—SiH₂(NEt₂))₃,N(SiH(NnPr₂)-CH₂—CH₂—SiH₂(NnPr₂))₃, N(SiH(NiPr₂)-CH₂—CH₂—SiH₂(NiPr₂))₃,N(SiH(NBu₂)-CH₂—CH₂—SiH₂(NBu₂))₃, N(SiH(NiBu₂)-CH₂—CH₂—SiH₂(NiBu₂))₃,N(SiH(NtBu₂)-CH₂—CH₂—SiH₂(NtBu₂))₃, N(SiH(NAm₂)-CH₂—CH₂—SiH₂(NAm₂))₃,N(SiH(NCyPentyl₂)-CH₂—CH₂—SiH₂(NCyPentyl₂))₃,N(SiH(Nhexyl₂)-CH₂—CH₂—SiH₂(Nhexyl₂))₃,N(SiH(NCyHexyl₂)-CH₂—CH₂—SiH₂(NCyHexyl₂))₃,N(SiH(NMeH)—CH₂—CH₂—SiH₂(NMeH))₃, N(SiH(NEtH)—CH₂—CH₂—SiH₂(NEtH))₃,N(SiH(NnPrH)—CH₂—CH₂—SiH₂(NnPrH))₃, N(SiH(NiPrH)—CH₂—CH₂—SiH₂(NiPrH))₃,N(SiH(NBuH)—CH₂—CH₂—SiH₂(NBuH))₃, N(SiH(NiBuH)—CH₂—CH₂—SiH₂(NiBuH))₃,N(SiH(NtBuH)—CH₂—CH₂—SiH₂(NtBuH))₃, N(SiH(NAmH)—CH₂—CH₂—SiH₂(NAmH))₃,N(SiH(pyridine)-CH₂—CH₂—SiH₂(pyridine))₃,N(SiH(pyrrole)-CH₂—CH₂—SiH₂(pyrrole))₃,N(SiH(pyrrolidine)-CH₂—CH₂—SiH₂(pyrrolidine))₃, andN(SiH(imidazole)-CH₂—CH₂—SiH₂(imidazole))₃.

Exemplary precursors presented in formula (III) wherein m=2, R³, R⁴ andR⁵═H include, but are not limited to, N(SiH₂—CH₂—CH₂—SiH(CH₂═CH)₂)₃,N(SiH₂—CH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NH₂)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NMe₂)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NMeEt)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NEt₂)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NnPr₂)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NiPr₂)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NBu₂)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NiBu₂)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NtBu₂)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NAm₂)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NCyPentyl₂)₂)₃,N(SiH₂—CH₂—CH₂—SiH(Nhexyl₂)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NCyHexyl₂)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NMeH)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NEtH)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NnPrH)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NiPrH)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NBuH)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NiBuH)₂)₃,N(SiH₂—CH₂—CH₂—SiH(NtBuH)₂)₃, N(SiH₂—CH₂—CH₂—SiH(NAmH)₂)₃,N(SiH₂—CH₂—CH₂—SiH(pyridine)₂)₃, N(SiH₂—CH₂—CH₂—SiH(pyrrole)₂)₃,N(SiH₂—CH₂—CH₂—SiH(pyrrolidine)₂)₃, andN(SiH₂—CH₂—CH₂—SiH(imidazole)₂)₃. These precursors may be suitable forvapor deposition or coating applications due at least partially to thebenefits discussed above for SiH bonds The terminal amino ligands mayalso provide improved thermal stability, as discussed above, as well asan additional N and/or C source for the resulting film. Finally, thelisted precursors having lower molecular weights and higher vaporpressures are better suited for vapor deposition techniques, whereasthose having higher molecular weights are better suited for coatingtechniques.

Exemplary precursors presented in formula (III) wherein m=2, R⁴ and R⁵═Hinclude, but are not limited to, N(SiH₂—CH₂—CH₂—Si—(CH₂═CH)₃)₃,N(SiH₂—CH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₃, N(SiH₂—CH₂—CH₂—Si(NH₂)₃)₃,N(SiH₂—CH₂—CH₂—Si(NMe₂)₃)₃, N(SiH₂—CH₂—CH₂—Si(NMeEt)₃)₃,N(SiH₂—CH₂—CH₂—Si(NEt₂)₃)_(3,) N(SiH₂—CH₂—CH₂—Si(NnPr₂)₃)₃,N(SiH₂—CH₂—CH₂—Si(NiPr₂)₃)₃, N(SiH₂—CH₂—CH₂—Si(NBu₂)₃)₃,N(SiH₂—CH₂—CH₂—Si(NiBu₂)₃)₃, N(SiH₂—CH₂—CH₂—Si(NtBu₂)₃)₃,N(SiH₂—CH₂—CH₂—Si(NAm₂)₃)₃, N(SiH₂—CH₂—CH₂—Si(NCyPentyl₂)₃)₃,N(SiH₂—CH₂—CH₂—Si(Nhexyl₂)₃)₃, N(SiH₂—CH₂—CH₂—Si(NCyHexyl₂)₃)₃,N(SiH₂—CH₂—CH₂—Si(NMeH)₃)₃, N(SiH₂—CH₂—CH₂—Si(NEtH)₃)₃,N(SiH₂—CH₂—CH₂—Si(NnPrH)₃)₃, N(SiH₂—CH₂—CH₂—Si(NiPrH)₃)₃,N(SiH₂—CH₂—CH₂—Si(NBuH)₃)₃, N(SiH₂—CH₂—CH₂—Si(NiBuH)₃)₃,N(SiH₂—CH₂—CH₂—Si(NtBuH)₃)₃, N(SiH₂—CH₂—CH₂—Si(NAmH)₃)₃₇N(SiH₂—CH₂—CH₂—Si(pyridine)₃)₃, N(SiH₂—CH₂—CH₂—Si(pyrrole)₃)₃,N(SiH₂—CH₂—CH₂—Si(pyrrolidine)₃)₃, and N(SiH₂—CH₂—CH₂—Si(imidazole)₃)₃.These precursors are suitable for coating applications due at leastpartially to the benefits discussed above for SiH bonds The terminalamino ligands may also provide an additional N and/or C source for theresulting film.

When a=1, the disclosed carbosilazane precursor presented in formula (I)has the following formula:

RN(SiR⁴R⁵(CH₂)_(m)SiR¹R²R³)₂   (IV)

When m=1 and R, R¹, R², R³, R⁴ and R⁵═H, the disclosed precursorpresented in formula (IV) is bis(1,3-disilapropane)amine[HN(SiH₂—CH₂—SiH₃)₂ or NDSP2]. NDSP2 is volatile and contains many Si—Hbonds, making it more reactive to the substrate surface. As a result,this precursor is suitable for vapor deposition processes and, moreparticularly, for ALD processes. Applicants believe that this precursormay even be sufficiently reactive to attach to Si—Cl terminated or evenSi terminated substrate surfaces in PEALD processes using N₂.

When m=1; R¹, R², R³, R⁴ and R⁵═H; and R═Si_(x)H_(2x+1), with x=1 to 4,the disclosed carbosilazane precursors presented in formula (IV) areSiH₃N(SiH₂—CH₂—SiH₃)₂, Si₂H₅N(SiH₂—CH₂—SiH₃)₂, Si₃H₇N(SiH₂—CH₂—SiH₃)₂,and Si₄H₉N(SiH₂—CH₂—SiH₃)₂. These precursors may be suitable for vapordeposition applications due at least partially to the benefits discussedabove for SiH bonds The additional N—Si bond makes these precursors morestable than those having a N—H bond, but more reactive than those havinga N—C bond. As a result, these precursors may be desirable when moderateconditions are required for polymerization. The carbon-freeSi_(x)H_(2x+1) may also result in more Si in the resulting film than thecorresponding molecules in which R═H or an alkyl group.

When m=1; R¹, R², R³, R⁴ and R⁵═H; and R═SiH_(z)(C_(y)H_(2y+1))_(3-z),with y=1 to 6, z=0 to 2, the disclosed carbosilazane precursor presentedin formula (IV) include, but are not limited to,(SiMe₃)N(SiH₂—CH₂—SiH₃)₂, (SiEt₃)N(SiH₂—CH₂—SiH₃)₂,Si(iPr)₃N(SiH₂—CH₂—SiH₃)₂, Si(nPr)₃N(SiH₂—CH₂—SiH₃)₂,Si(Bu)₃N(SiH₂—CH₂—SiH₃)₂, Si(iBu)₃N(SiH₂—CH₂—SiH₃)₂,Si(tBu)₃N(SiH₂—CH₂—SiH₃)₂, Si(amyl)₃N(SiH₂—CH₂—SiH₃)₂,Si(hexyl)₃N(SiH₂—CH₂—SiH₃)₂, (SiHMe₂)N(SiH₂—CH₂—SiH₃)₂,(SiHEt₂)N(SiH₂—CH₂—SiH₃)₂, SiH(iPr)₂N(SiH₂—CH₂—SiH₃)₂,SiH(nPr)₂N(SiH₂—CH₂—SiH₃)₂, SiH(Bu)₂N(SiH₂—CH₂—SiH₃)₂,SiH(iBu)₂N(SiH₂—CH₂—SiH₃)₂, SiH(tBu)₂N(SiH₂—CH₂—SiH₃)₂,SiH(amyl)₂N(SiH₂—CH₂—SiH₃)₂, SiH(hexyl)₂N(SiH₂—CH₂—SiH₃)₂,(SiH₂Me)N(SiH₂—CH₂—SiH₃)₂, (SiH₂Et)N(SiH₂—CH₂—SiH₃)₂,SiH₂(iPr)N(SiH₂—CH₂—SiH₃)₂, SiH₂(nPr)N(SiH₂—CH₂—SiH₃)₂,SiH₂(Bu)N(SiH₂—CH₂—SiH₃)₂, SiH₂(iBu)N(SiH₂—CH₂—SiH₃)₂,SiH₂(tBu)N(SiH₂—CH₂—SiH₃)₂, SiH₂(amyl)N(SiH₂—CH₂—SiH₃)₂, andSiH₂(hexyl)N(SiH₂—CH₂—SiH₃)₂. The additional N—Si bond makes theseprecursors more stable than those having a N—H bond, but more reactivethan those having a N—C bond. As a result, these precursors may bedesirable when moderate conditions are required for polymerization. Thelength of the carbon chain may be selected to provide the desired amountof carbon in the film. Finally, the listed precursors having lowermolecular weights and higher vapor pressures are better suited for vapordeposition techniques, whereas those having higher molecular weights arebetter suited for coating techniques.

When m=1; R¹, R², R³, R⁴ and R⁵═H; and R=aR^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group with b=1 to 2 andR^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) independently H or a C₁-C₆hydrocarbon group, the disclosed carbosilazane precursors presented informula (IV) include, but are not limited to(SiH₃—CH₂—CH₂—SiH₂)N(SiH₂—CH₂—SiH₃)₂,(SiMe₃-CH₂—SiMe₂)N(SiH₂—CH₂—SiH₃)₂,(SiMe₃-CH₂—CH₂—SiMe₂)N(SiH₂—CH₂—SiH₃)₂,(SiEt₃-CH₂—SiEt₂)N(SiH₂—CH₂—SiH₃)₂, or(SiEt₃-CH₂—CH₂—SiEt₂)N(SiH₂—CH₂—SiH₃)₂.

When m=1; R¹, R², R³, R⁴ and R⁵═H; and R═C_(y)H_(2y+1), with y=1 to 6,the disclosed carbosilazane precursors presented in formula (IV) include(Me)N(SiH₂—CH₂—SiH₃)₂, (Et)N(SiH₂—CH₂—SiH₃)₂, (nPr)N(SiH₂—CH₂—SiH₃)₂,(iPr)N(SiH₂—CH₂—SiH₃)₂, (Bu)N(SiH₂—CH₂—SiH₃)₂, (iBu)N(SiH₂—CH₂—SiH₃)₂,(tBu)N(SiH₂—CH₂—SiH₃)₂, (amyl)N(SiH₂—CH₂—SiH₃)₂, and(hexyl)N(SiH₂—CH₂—SiH₃)₂. This family of compounds may be useful forvapor deposition of films having carbon content, such as SiOC or SiNC,because the Si—C bond (for Si—R) is not highly reactive and is likely toremain intact during the deposition process. As a result, to preventdeposition of too much C, y is preferably 1 to 3. These precursors arealso easier to synthesize than the DSP3 analogs because the RNHR₂reactant is a liquid for Et, Pr, Bu, Pentyl, and Hexyl.

When m=1; R¹, R², R³, R⁴ and R⁵═H; and R═C_(x)H_(2x-y), with x=2 to 6,y=0 for x=2-6 or y=2 for x=3-6 or y=4 for x=4-6 the disclosedcarbosilazane precursors presented in formula (IV) include(Vinyl)N(SiH₂—CH₂—SiH₃)₂, (Allyl)N(SiH₂—CH₂—SiH₃)₂,(propadiene)N(SiH₂—CH₂—SiH₃)₂, (butene)N(SiH₂—CH₂—SiH₃)₂,(butadiene)N(SiH₂—CH₂—SiH₃)₂, (butatriene)N(SiH₂—CH₂—SiH₃)₂., or(hexadiene)N(SiH₂—CH₂—SiH₃)₂. This family of compounds may be alsouseful for vapor deposition of films having carbon content.Additionally, the unsaturated hydrocarbon provides cross-linkingopportunities between the chemi- or physio-sorbed precursors.

When m=1; R¹, R², R³, R⁴ and R⁵═H; and R═SiH_(x)(NR′R″)_(3-x) with x=1or 2 and R′ and R″ independently Me, Et, iPr, or nPr, the disclosedcarbosilazane precursors presented in formula (IV) include, but are notlimited to, (SiH₂NMe₂)N(SiH₂—CH₂—SiH₃)₂, (SiH₂NEt₂)N(SiH₂—CH₂—SiH₃)₂,(SiH₂NiPr₂)N(SiH₂—CH₂—SiH₃)₂, (SiH₂NnPr₂)N(SiH₂—CH₂—SiH₃)₂,(SiH₂NMeEt)N(SiH₂—CH₂—SiH₃)₂, (SiH(NMe₂)₂)N(SiH₂—CH₂—SiH₃)₂, andSiH(NEt₂)₂)N(SiH₂—CH₂—SiH₃)₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=1; R¹, R², R³ and R⁴═H; and R═H, C_(u)H_(2u+1), or Si_(v)H_(2v-1),with u=1-6 and v=1-4, include, but are not limited to,RN(SiH(CH₂═CH)—CH₂—SiH₃)₂, RN(SiH(CH₂═CH—CH₂)—CH₂—SiH₃)₂,RN(SiH(NH₂)—CH₂—SiH₃)₂, RN(SiH(NMe₂)-CH₂—SiH₃)₂,RN(SiH(NMeEt)-CH₂—SiH₃)₂, RN(SiH(NEt₂)-CH₂—SiH₃)₂,RN(SiH(NnPr₂)-CH₂—SiH₃)₂, RN(SiH(NiPr₂)-CH₂—SiH₃)₂,RN(SiH(NBu₂)-CH₂—SiH₃)₂, RN(SiH(NiBu₂)-CH₂—SiH₃)₂,RN(SiH(NtBu₂)-CH₂—SiH₃)₂, RN(SiH(NAm₂)-CH₂—SiH₃)₂,RN(SiH(NCyPentyl₂)-CH₂—SiH₃)₂, RN(SiH(Nhexyl₂)-CH₂—SiH₃)₂,RN(SiH(NCyHexyl₂)-CH₂—SiH₃)₂, RN(SiH(NMeH)—CH₂—SiH₃)₂,RN(SiH(NEtH)—CH₂—SiH₃)₂, RN(SiH(NnPrH)—CH₂—SiH₃)₂,RN(SiH(NiPrH)—CH₂—SiH₃)₂, RN(SiH(NBuH)—CH₂—SiH₃)₂,RN(SiH(NiBuH)—CH₂—SiH₃)₂, RN(SiH(NtBuH)—CH₂—SiH₃)₂,RN(SiH(NAmH)—CH₂—SiH₃)₂, RN(SiH(pyridine)-CH₂—SiH₃)₂,RN(SiH(pyrrole)-CH₂—SiH₃)₂, RN(SiH(pyrrolidine)-CH₂—SiH₃)₂, andRN(SiH(imidazole)-CH₂—SiH₃)₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=1; R², R³, R⁴ and R⁵═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), withu=1-6 and v=1-4, include, but are not limited to,RN(SiH₂—CH₂—SiH₂(CH₂═CH))₂, RN(SiH₂—CH₂—SiH₂(CH₂═CH—CH₂))₂,RN(SiH₂—CH₂—SiH₂(NH₂))₂, RN(SiH₂—CH₂—SiH₂(NMe₂))₂,RN(SiH₂—CH₂—SiH₂(NMeEt))₂, RN(SiH₂—CH₂—SiH₂(NEt₂))₂,RN(SiH₂—CH₂—SiH₂(NnPr₂))₂, RN(SiH₂—CH₂—SiH₂(NiPr₂))₂,RN(SiH₂—CH₂—SiH₂(NBu₂))₂, RN(SiH₂—CH₂—SiH₂(NiBu₂))₂,RN(SiH₂—CH₂—SiH₂(NtBu₂))₂, RN(SiH₂—CH₂—SiH₂(NAm₂))₂,RN(SiH₂—CH₂—SiH₂(NCyPentyl₂))₂, RN(SiH₂—CH₂—SiH₂(Nhexyl₂))₂,RN(SiH₂—CH₂—SiH₂(NCyHexyl₂))₂, RN(SiH₂—CH₂—SiH₂(NMeH))₂,RN(SiH₂—CH₂—SiH₂(NEtH))₂, RN(SiH₂—CH₂—SiH₂(NnPrH))₂,RN(SiH₂—CH₂—SiH₂(NiPrH))₂, RN(SiH₂—CH₂—SiH₂(NBuH))₂,RN(SiH₂—CH₂—SiH₂(NiBuH))₂, RN(SiH₂—CH₂—SiH₂(NtBuH))₂,RN(SiH₂—CH₂—SiH₂(NAmH))₂, RN(SiH₂—CH₂—SiH₂(pyridine))₂,RN(SiH₂—CH₂—SiH₂(pyrrole))₂, RN(SiH₂—CH₂—SiH₂(pyrrolidine))₂, andRN(SiH₂—CH₂—SiH₂(imidazole))₂. These precursors may be suitable forvapor deposition or coating applications due at least partially to thebenefits discussed above for SiH bonds The terminal amino ligands mayalso provide improved thermal stability, as discussed above, as well asan additional N and/or C source for the resulting film. Finally, thelisted precursors having lower molecular weights and higher vaporpressures are better suited for vapor deposition techniques, whereasthose having higher molecular weights are better suited for coatingtechniques.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=1; R¹, R² and R³═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), with u=1-6and v=1-4, include, but are not limted to, RN(Si—(CH₂═CH)₂—CH₂—SiH₃)₂,RN(Si—(CH₂═CH—CH₂)₂—CH₂—SiH₃)₂, RN(Si(NH₂)₂—CH₂—SiH₃)₂,RN(Si(NMe₂)₂-CH₂—SiH₃)₂, RN(Si(NMeEt)₂-CH₂—SiH₃)₂, RN(SiNEt₂-CH₂—SiH₃)₂,RN(Si(NnPr₂)₂-CH₂—SiH₃)₂, RN(Si(NiPr₂)₂-CH₂—SiH₃)₂,RN(Si(NBu₂)₂-CH₂—SiH₃)₂, RN(Si(NiBu₂)₂-CH₂—SiH₃)₂,RN(Si(NtBu₂)₂-CH₂—SiH₃)₂, RN(Si(NAm₂)₂-CH₂—SiH₃)₂,RN(Si(NCyPentyl₂)₂-CH₂—SiH₃)₂, RN(Si(Nhexyl₂)₂-CH₂—SiH₃)₂,RN(Si(NCyHexyl₂)₂-CH₂—SiH₃)₂, RN(Si(NMeH)₂—CH₂—SiH₃)₂,RN(Si(NEtH)₂—CH₂—SiH₃)₂, RN(Si(NnPrH)₂—CH₂—SiH₃)₂,RN(Si(NiPrH)₂—CH₂—SiH₃)₂, RN(Si(NBuH)₂—CH₂—SiH₃)₂,RN(Si(NiBuH)₂—CH₂—SiH₃)₂, RN(Si(NtBuH)₂—CH₂—SiH₃)₂,RN(Si(NAmH)₂—CH₂—SiH₃)₂, RN(Si(pyridine)₂-CH₂—SiH₃)₂,RN(Si(pyrrole)₂-CH₂—SiH₃)₂, RN(Si(pyrrolidine)₂-CH₂—SiH₃)₂, andRN(Si(imidazole)₂-CH₂—SiH₃)₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=1; R², R³ and R⁴═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), with u=1-6and v=1-4, include RN(SiH(CH₂═CH)—CH₂—SiH₂(CH₂═CH))₂,RN(SiH(CH₂═CH—CH₂)—CH₂—SiH₂(CH₂═CH—CH₂))₂, RN(SiH(NH₂)—CH₂—SiH₂(NH₂))₂,RN(SiH(NMe₂)-CH₂—SiH₂(NMe₂))₂, RN(SiH(NMeEt)-CH₂—SiH₂(NMeEt))₂,RN(SiH(NEt₂)-CH₂—SiH₂(NEt₂))₂, RN(SiH(NnPr₂)-CH₂—SiH₂(NnPr₂))₂,RN(SiH(NiPr₂)-CH₂—SiH₂(NiPr₂))₂, RN(SiH(NBu₂)-CH₂—SiH₂(NBu₂))₂,RN(SiH(NiBu₂)-CH₂—SiH₂(NiBu₂))₂, RN(SiH(NtBu₂)-CH₂—SiH₂(NtBu₂))₂,RN(SiH(NAm₂)-CH₂—SiH₂(NAm₂))₂,RN(SiH(NCyPentyl₂)-CH₂—SiH₂(NCyPentyl₂))₂,RN(SiH(Nhexyl₂)-CH₂—SiH₂(Nhexyl₂))₂,RN(SiH(NCyHexyl₂)-CH₂—SiH₂(NCyHexyl₂))₂, RN(SiH(NMeH)—CH₂—SiH₂(NMeH))₂,RN(SiH(NEtH)—CH₂—SiH₂(NEtH))₂, RN(SiH(NnPrH)—CH₂—SiH₂(NnPrH))₂,RN(SiH(NiPrH)—CH₂—SiH₂(NiPrH))₂, RN(SiH(NBuH)—CH₂—SiH₂(NBuH))₂,RN(SiH(NiBuH)—CH₂—SiH₂(NiBuH))₂, RN(SiH(NtBuH)—CH₂—SiH₂(NtBuH))₂,RN(SiH(NAmH)—CH₂—SiH₂(NAmH))₂, RN(SiH(pyridine)-CH₂—SiH₂(pyridine))₂,RN(SiH(pyrrole)-CH₂—SiH₂(pyrrole))₂,RN(SiH(pyrrolidine)-CH₂—SiH₂(pyrrolidine))₂, andRN(SiH(imidazole)-CH₂—SiH₂(imidazole))₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=1; R³, R⁴ and R⁵═H; R═H, C_(u)H_(2u+1), or SivH_(2v-1), with u=1-6 andv=1-4, include, but are not limited to, RN(SiH₂—CH₂—SiH(CH₂═CH)₂)₂,RN(SiH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₂, RN(SiH₂—CH₂—SiH(NH₂)₂)₂,RN(SiH₂—CH₂—SiH(NMe₂)₂)₂, RN(SiH₂—CH₂—SiH(NMeEt)₂)₂,RN(SiH₂—CH₂—SiH(NEt₂)₂)₂, RN(SiH₂—CH₂—SiH(NnPr₂)₂)₂,RN(SiH₂—CH₂—SiH(NiPr₂)₂)₂, RN(SiH₂—CH₂—SiH(NBu₂)₂)₂,RN(SiH₂—CH₂—SiH(NiBu₂)₂)₂, RN(SiH₂—CH₂—SiH(NtBu₂)₂)₂,RN(SiH₂—CH₂—SiH(NAm₂)₂)₂, RN(SiH₂—CH₂—SiH(NCyPentyl₂)₂)₂,RN(SiH₂—CH₂—SiH(Nhexyl₂)₂)₂, RN(SiH₂—CH₂—SiH(NCyHexyl₂)₂)₂,RN(SiH₂—CH₂—SiH(NMeH)₂)₂, RN(SiH₂—CH₂—SiH(NEtH)₂)₂,RN(SiH₂—CH₂—SiH(NnPrH)₂)₂, RN(SiH₂—CH₂—SiH(NiPrH)₂)₂,RN(SiH₂—CH₂—SiH(NBuH)₂)₂, RN(SiH₂—CH₂—SiH(NiBuH)₂)₂,RN(SiH₂—CH₂—SiH(NtBuH)₂)₂, RN(SiH₂—CH₂—SiH(NAmH)₂)₂,RN(SiH₂—CH₂—SiH(pyridine)₂)₂, RN(SiH₂—CH₂—SiH(pyrrole)₂)₂,RN(SiH₂—CH₂—SiH(pyrrolidine)₂)₂, and RN(SiH₂—CH₂—SiH(imidazole)₂)₂.These precursors are suitable for vapor deposition or coatingapplications due at least partially to the benefits discussed above forSiH bonds The terminal amino ligands may also provide improved thermalstability, as discussed above, as well as an additional N and/or Csource for the resulting film. Finally, the listed precursors havinglower molecular weights and higher vapor pressures are better suited forvapor deposition techniques, whereas those having higher molecularweights are better suited for coating techniques.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=1; R⁴ and R⁵═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), with u=1-6 andv=1-4, include, but are not limited to, RN(SiH₂—CH₂—Si—(CH₂═CH)₃)₂,RN(SiH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₂, RN(SiH₂—CH₂—Si(NH₂)₃)₂,RN(SiH₂—CH₂—Si(NMe₂)₃)₂, RN(SiH₂—CH₂—Si(NMeEt)₃)₂,RN(SiH₂—CH₂—Si(NEt₂)₃)₂, RN(SiH₂—CH₂—Si(NnPr₂)₃)₂,RN(SiH₂—CH₂—Si(NiPr₂)₃)₂, RN(SiH₂—CH₂—Si(NBu₂)₃)₂,RN(SiH₂—CH₂—Si(NiBu₂)₃)₂, RN(SiH₂—CH₂—Si(NtBu₂)₃)₂,RN(SiH₂—CH₂—Si(NAm₂)₃)₂, RN(SiH₂—CH₂—Si(NCyPentyl₂)₃)₂,RN(SiH₂—CH₂—Si(Nhexyl₂)₃)₂, RN(SiH₂—CH₂—Si(NCyHexyl₂)₃)₂,RN(SiH₂—CH₂—Si(NMeH)₃)₂, RN(SiH₂—CH₂—Si(NEtH)₃)₂,RN(SiH₂—CH₂—Si(NnPrH)₃)₂, RN(SiH₂—CH₂—Si(NiPrH)₃)₂,RN(SiH₂—CH₂—Si(NBuH)₃)₂, RN(SiH₂—CH₂—Si(NiBuH)₃)₂,RN(SiH₂—CH₂—Si(NtBuH)₃)₂, RN(SiH₂—CH₂—Si(NAmH)₃)₂,RN(SiH₂—CH₂—Si(pyridine)₃)₂, RN(SiH₂—CH₂—Si(pyrrole)₃)₂,RN(SiH₂—CH₂—Si(pyrrolidine)₃)₂, and RN(SiH₂—CH₂—Si(imidazole)₃)₂. Theseprecursors may be suitable vapor deposition or coating applications dueat least partially to the benefits discussed above for SiH bonds Theterminal amino ligands may also provide improved thermal stability, asdiscussed above, as well as an additional N and/or C source for theresulting film. Finally, the listed precursors having lower molecularweights and higher vapor pressures are better suited for vapordeposition techniques, whereas those having higher molecular weights arebetter suited for coating techniques.

When m=2 and R, R¹, R², R³, R⁴ and R⁵═H, the disclosed carbosilazaneprecursor is HN(SiH₂—CH₂—CH₂—SiH₃)₂ (HNDSB2). HNDSB2 is volatile andcontains many Si—H bonds, making it more reactive to the substratesurface. As a result, this precursor may be suitable for vapordeposition processes and, more particularly, for ALD processes.Applicants believe that this precursor may even be sufficiently reactiveto attach to Si—Cl terminated or even Si terminated substrate surfacesin PEALD processes using N₂.

When m=2; R¹, R², R³, R⁴ and R⁵═H; and R═Si_(x)H_(2x+1), with x=1 to 4,the disclosed carbosilazane precursors presented in formula (IV) areSiH₃N(SiH₂—CH₂—CH₂—SiH₃)₂, Si₂H₅N(SiH₂—CH₂—CH₂—SiH₃)₂,Si₃H₇N(SiH₂—CH₂—CH₂—SiH₃)₂, and Si₄H₉N(SiH₂—CH₂—CH₂—SiH₃)₂. Theseprecursors may be suitable for vapor deposition applications due atleast partially to the benefits discussed above for SiH bonds. Theadditional N—Si bond makes these precursors more stable than thosehaving a N—H bond, but more reactive than those having a N—C bond. As aresult, these precursors may be desirable when moderate conditions arerequired for polymerization. The carbon-free Si_(x)H_(2x+1) may alsoresult in more Si in the resulting film than the corresponding moleculesin which R═H or an alkyl group.

When m=2; R¹, R², R³, R⁴ and R⁵═H; and R═SiH_(z)(C_(y)H_(2y+1))_(3-z),with y=1 to 6, z=0 to 2, the disclosed carbosilazane precursor presentedin formula (IV) include, but are not limited to(SiMe₃)N(SiH₂—CH₂—CH₂—SiH₃)₂, (SiEt₃)N(SiH₂—CH₂—CH₂—SiH₃)₂,Si(iPr)₃N(SiH₂—CH₂—CH₂—SiH₃)₂, Si(nPr)₃N(SiH₂—CH₂—CH₂—SiH₃)₂,Si(Bu)₃N(SiH₂—CH₂—CH₂—SiH₃)₂, Si(iBu)₃N(SiH₂—CH₂—CH₂—SiH₃)₂,Si(tBu)₃N(SiH₂—CH₂—CH₂—SiH₃)₂, Si(amyl)₃N(SiH₂—CH₂—CH₂—SiH₃)₂,Si(hexyl)₃N(SiH₂—CH₂—CH₂—SiH₃)₂, (SiHMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiHEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂, SiH(iPr)₂N(SiH₂—CH₂—CH₂—SiH₃)₂,SiH(nPr)₂N(SiH₂—CH₂—CH₂—SiH₃)₂, SiH(Bu)₂N(SiH₂—CH₂—CH₂—SiH₃)₂,SiH(iBu)₂N(SiH₂—CH₂—CH₂—SiH₃)₂, SiH(tBu)₂N(SiH₂—CH₂—CH₂—SiH₃)₂,SiH(amyl)₂N(SiH₂—CH₂—CH₂—SiH₃)₂, SiH(hexyl)₂N(SiH₂—CH₂—CH₂—SiH₃)₂,SiH₂Me₂)N(SiH₂—CH₂—CH₂—SiH₃)₂, (SiH₂Et₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,SiH₂(iPr)N(SiH₂—CH₂—CH₂—SiH₃)₂, SiH₂(nPr)N(SiH₂—CH₂—CH₂—SiH₃)₂,SiH₂(Bu)N(SiH₂—CH₂—CH₂—SiH₃)₂, SiH₂(iBu)N(SiH₂—CH₂—CH₂—SiH₃)₂,SiH₂(tBu)N(SiH₂—CH₂—CH₂—SiH₃)₂, SiH₂(amyl)N(SiH₂—CH₂—CH₂—SiH₃)₂, andSiH₂(hexyl)N(SiH₂—CH₂—CH₂—SiH₃)₂. The additional N—Si bond makes theseprecursors more stable than those having a N—H bond, but more reactivethan those having a N—C bond. As a result, these precursors may bedesirable when moderate conditions are required for polymerization. Thelength of the carbon chain may be selected to provide the desired amountof carbon in the film. Finally, the listed precursors having lowermolecular weights and higher vapor pressures are better suited for vapordeposition techniques, whereas those having higher molecular weights arebetter suited for coating techniques.

When m=2; R¹, R², R³, R⁴ and R⁵═H; and R=aR^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group, with b=1 to 2 andR^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) are independently H or aC₁-C₆ hydrocarbon group, the disclosed carbosilazane precursorspresented in formula (IV) include, but are not limited to,(SiH₃—CH₂—SiH₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiH₃—CH₂—CH₂—SiH₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiMe₃-CH₂—SiMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiMe₃-CH₂—CH₂—SiMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiEt₃-CH₂—SiEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂, and(SiEt₃-CH₂—CH₂—SiEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂.

When m=2; R¹, R², R³, R⁴ and R⁵═H; and R═C_(y)H_(2y+1), with y=1 to 6,the disclosed carbosilazane precursors presented in formula (IV)include, but are not limited to, (Me)N(SiH₂—CH₂—CH₂—SiH₃)₂,(Et)N(SiH₂—CH₂—CH₂—SiH₃)₂, (nPr)N(SiH₂—CH₂—CH₂—SiH₃)₂,(iPr)N(SiH₂—CH₂—CH₂—SiH₃)₂, (Bu)N(SiH₂—CH₂—CH₂—SiH₃)₂,(iBu)N(SiH₂—CH₂—CH₂—SiH₃)₂, (tBu)N(SiH₂—CH₂—CH₂—SiH₃)₂,(amyl)N(SiH₂—CH₂—CH₂—SiH₃)₂, and (hexyl)N(SiH₂—CH₂—CH₂—SiH₃)₂. Thisfamily of compounds may be useful for vapor deposition of films havingcarbon content, such as SiOC or SiNC, because the Si—C bond (for Si—R)is not highly reactive and is likely to remain intact during thedeposition process. As a result, to prevent deposition of too much C, yis preferably 1 to 3. These precursors are also easier to synthesizethan the DSB3 analogs because the RNHR₂ reactant is a liquid for Et, Pr,Bu, Pentyl, and Hexyl.

When m=2; R¹, R², R³, R⁴ and R⁵═H; and R═SiH_(x)(NR′R″)_(3-x) with x=1or 2 and R′ and R″ independently Me, Et, iPr, nPr, the disclosedcarbosilazane precursors presented in formula (IV) include, but are notlimited to, (SiH₂NMe₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiH₂NEt₂)N(SiH₂—CH₂—CH₂—SiH₃)₂, (SiH₂NiPr₂)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiH₂NnPr₂)N(SiH₂—CH₂—CH₂—SiH₃)₂, (SiH₂NMeEt)N(SiH₂—CH₂—CH₂—SiH₃)₂,(SiH(NMe₂)₂)N(SiH₂—CH₂—CH₂—SiH₃)₂, and SiH(NEt₂)₂)N(SiH₂—CH₂—CH₂—SiH₃)₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=2; R¹, R², R³ and R⁴═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), withu=1-6 and v=1-4, include, but are not limited to,RN(SiH(CH₂═CH)—CH₂—CH₂—SiH₃)₂, RN(SiH(CH₂═CH—CH₂)—CH₂—CH₂—SiH₃)₂,RN(SiH(NH₂)—CH₂—CH₂—SiH₃)₂, RN(SiH(NMe₂)-CH₂—CH₂—SiH₃)₂,RN(SiH(NMeEt)-CH₂—CH₂—SiH₃)₂, RN(SiH(NEt₂)-CH₂—CH₂—SiH₃)₂,RN(SiH(NnPr₂)-CH₂—CH₂—SiH₃)₂, RN(SiH(NiPr₂)-CH₂—CH₂—SiH₃)₂,RN(SiH(NBu₂)-CH₂—CH₂—SiH₃)₂, RN(SiH(NiBu₂)-CH₂—CH₂—SiH₃)₂,RN(SiH(NtBu₂)-CH₂—CH₂—SiH₃)₂, RN(SiH(NAm₂)-CH₂—CH₂—SiH₃)₂,RN(SiH(NCyPentyl₂)-CH₂—CH₂—SiH₃)₂, RN(SiH(Nhexyl₂)-CH₂—CH₂—SiH₃)₂,RN(SiH(NCyHexyl₂)-CH₂—CH₂—SiH₃)₂, RN(SiH(NMeH)—CH₂—CH₂—SiH₃)₂,RN(SiH(NEtH)—CH₂—CH₂—SiH₃)₂, RN(SiH(NnPrH)—CH₂—CH₂—SiH₃)₂,RN(SiH(NiPrH)—CH₂—CH₂—SiH₃)₂, RN(SiH(NBuH)—CH₂—CH₂—SiH₃)₂,RN(SiH(NiBuH)—CH₂—CH₂—SiH₃)₂, RN(SiH(NtBuH)—CH₂—CH₂—SiH₃)₂,RN(SiH(NAmH)—CH₂—CH₂—SiH₃)₂, RN(SiH(pyridine)-CH₂—CH₂—SiH₃)₂,RN(SiH(pyrrole)-CH₂—CH₂—SiH₃)₂, RN(SiH(pyrrolidine)-CH₂—CH₂—SiH₃)₂, andRN(SiH(imidazole)-CH₂—CH₂—SiH₃)₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=2; R², R³, R⁴ and R⁵═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), withu=1-6 and v=1-4, include, but are not limited to,RN(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH))₂, RN(SiH₂—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NH₂))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NMe₂))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NMeEt))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NEt₂))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NnPr₂))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NiPr₂))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NBu₂))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NiBu₂))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NtBu₂))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NAm₂))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NCyPentyl₂))₂, RN(SiH₂—CH₂—CH₂—SiH₂(Nhexyl₂))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NCyHexyl₂))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NMeH))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NEtH))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NnPrH))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NiPrH))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NBuH))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NiBuH))₂, RN(SiH₂—CH₂—CH₂—SiH₂(NtBuH))₂,RN(SiH₂—CH₂—CH₂—SiH₂(NAmH))₂, RN(SiH₂—CH₂—CH₂—SiH₂(pyridine))₂,RN(SiH₂—CH₂—CH₂—SiH₂(pyrrole))₂, RN(SiH₂—CH₂—CH₂—SiH₂(pyrrolidine))₂,and RN(SiH₂—CH₂—CH₂—SiH₂(imidazole))₂. These precursors are suitable foreither vapor deposition or coating applications due at least partiallyto the benefits discussed above for SiH bonds The terminal amino ligandsmay also provide improved thermal stability, as discussed above, as wellas an additional N and/or C source for the resulting film. Finally, thelisted precursors having lower molecular weights and higher vaporpressures are better suited for vapor deposition techniques, whereasthose having higher molecular weights are better suited for coatingtechniques.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=2; R¹, R² and R³═H; and R═H, C_(u)H_(2u+1), or Si_(v)H_(2v-1), withu=1-6 and v=1-4, include, but are not limited to,RN(Si—(CH₂═CH)₂—CH₂—CH₂—SiH₃)₂, RN(Si—(CH₂═CH—CH₂)₂—CH₂—CH₂—SiH₃)₂,RN(Si(NH₂)₂—CH₂—CH₂—SiH₃)₂, RN(Si(NMe₂)₂—CH₂—CH₂—SiH₃)₂,RN(Si(NMeEt)₂-CH₂—CH₂—SiH₃)₂, RN(Si(NEt₂)₂-CH₂—CH₂—SiH₃)₂,RN(Si(NnPr₂)₂-CH₂—CH₂—SiH₃)₂, RN(Si(NiPr₂)₂-CH₂—CH₂—SiH₃)₂,RN(Si(NBu₂)₂-CH₂—CH₂—SiH₃)₂, RN(Si(NiBu₂)₂-CH₂—CH₂—SiH₃)₂,RN(Si(NtBu₂)₂-CH₂—CH₂—SiH₃)₂, RN(Si(NAm₂)₂-CH₂—CH₂—SiH₃)₂,RN(Si(NCyPentyl₂)₂-CH₂—CH₂—SiH₃)₂, RN(Si(Nhexyl₂)₂-CH₂—CH₂—SiH₃)₂,RN(Si(NCyHexyl₂)₂-CH₂—CH₂—SiH₃)₂, RN(Si(NMeH)₂—CH₂—CH₂—SiH₃)₂,RN(Si(NEtH)₂—CH₂—CH₂—SiH₃)₂, RN(Si(NnPrH)₂—CH₂—CH₂—SiH₃)₂,RN(Si(NiPrH)₂—CH₂—CH₂—SiH₃)₂, RN(Si(NBuH)₂—CH₂—CH₂—SiH₃)₂,RN(Si(NiBuH)₂—CH₂—CH₂—SiH₃)₂, RN(Si(NtBuH)₂—CH₂—CH₂—SiH₃)₂,RN(Si(NAmH)₂—CH₂—CH₂—SiH₃)₂, RN(Si(pyridine)₂-CH₂—CH₂—SiH₃)₂,RN(Si(pyrrole)₂-CH₂—CH₂—SiH₃)₂, RN(Si(pyrrolidine)₂-CH₂—CH₂—SiH₃)₂, andRN(Si(imidazole)₂-CH₂—CH₂—SiH₃)₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=2; R², R³ and R⁴═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), with u=1-6and v=1-4, include, but are not limited to,RN(SiH(CH₂═CH)—CH₂—CH₂—SiH₂(CH₂═CH))₂,RN(SiH(CH₂═CH—CH₂)—CH₂—CH₂—SiH₂(CH₂═CH—CH₂))₂,RN(SiH(NH₂)—CH₂—CH₂—SiH₂(NH₂))₂, RN(SiH(NMe₂)-CH₂—CH₂—SiH₂(NMe₂))₂,RN(SiH(NMeEt)-CH₂—CH₂—SiH₂(NMeEt))₂, RN(SiH(NEt₂)-CH₂—CH₂—SiH₂(NEt₂))₂,RN(SiH(NnPr₂)-CH₂—CH₂—SiH₂(NnPr₂))₂,RN(SiH(NiPr₂)-CH₂—CH₂—SiH₂(NiPr₂))₂, RN(SiH(NBu₂)-CH₂—CH₂—SiH₂(NBu₂))₂,RN(SiH(NiBu₂)-CH₂—CH₂—SiH₂(NiBu₂))₂,RN(SiH(NtBu₂)-CH₂—CH₂—SiH₂(NtBu₂))₂, RN(SiH(NAm₂)-CH₂—CH₂—SiH₂(NAm₂))₂,RN(SiH(NCyPentyl₂)-CH₂—CH₂—SiH₂(NCyPentyl₂))₂,RN(SiH(Nhexyl₂)-CH₂—CH₂—SiH₂(Nhexyl₂))₂,RN(SiH(NCyHexyl₂)-CH₂—CH₂—SiH₂(NCyHexyl₂))₂,RN(SiH(NMeH)—CH₂—CH₂—SiH₂(NMeH))₂, RN(SiH(NEtH)—CH₂—CH₂—SiH₂(NEtH))₂,RN(SiH(NnPrH)—CH₂—CH₂—SiH₂(NnPrH))₂,RN(SiH(NiPrH)—CH₂—CH₂—SiH₂(NiPrH))₂, RN(SiH(NBuH)—CH₂—CH₂—SiH₂(NBuH))₂,RN(SiH(NiBuH)—CH₂—CH₂—SiH₂(NiBuH))₂,RN(SiH(NtBuH)—CH₂—CH₂—SiH₂(NtBuH))₂, RN(SiH(NAmH)—CH₂—CH₂—SiH₂(NAmH))₂,RN(SiH(pyridine)-CH₂—CH₂—SiH₂(pyridine))₂,RN(SiH(pyrrole)-CH₂—CH₂—SiH₂(pyrrole))₂,RN(SiH(pyrrolidine)-CH₂—CH₂—SiH₂(pyrrolidine))₂, andRN(SiH(imidazole)-CH₂—CH₂—SiH₂(imidazole))₂.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=2; R³, R⁴ and R⁵═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), with u=1-6and v=1-4, include, but are not limited to,RN(SiH₂—CH₂—CH₂—SiH(CH₂═CH)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(CH₂═CH—CH₂)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NH₂)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NMe₂)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NMeEt)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NEt₂)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NnPr₂)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NiPr₂)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NBu₂)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NiBu₂)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NtBu₂)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NAm₂)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NCyPentyl₂)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(Nhexyl₂)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NCyHexyl₂)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NMeH)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NEtH)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NnPrH)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NiPrH)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NBuH)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NiBuH)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(NtBuH)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(NAmH)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(pyridine)₂)₂,RN(SiH₂—CH₂—CH₂—SiH(pyrrole)₂)₂, RN(SiH₂—CH₂—CH₂—SiH(pyrrolidine)₂)₂,and RN(SiH₂—CH₂—CH₂—SiH(imidazole)₂)₂. These precursors are suitable forvapor deposition or coating applications due at least partially to thebenefits discussed above for SiH bonds The terminal amino ligands mayalso provide improved thermal stability, as discussed above, as well asan additional N and/or C source for the resulting film. Finally, thelisted precursors having lower molecular weights and higher vaporpressures are better suited for vapor deposition techniques, whereasthose having higher molecular weights are better suited for coatingtechniques.

Exemplary carbosilazane precursors presented in formula (IV) whereinm=2; R⁴ and R⁵═H; and R═H, C_(u)H_(2u+1), or SivH_(2v-1), with u=1-6 andv=1-4, include, but are not limited to, RN(SiH₂—CH₂—CH₂—Si—(CH₂═CH)₃)₂,RN(SiH₂—CH₂—CH₂—Si—(CH₂═CH—CH₂)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NH₂)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NMe₂)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NMeEt)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NEt₂)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NnPr₂)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NiPr₂)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NBu₂)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NiBu₂)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NtBu₂)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NAm₂)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NCyPentyl₂)₃)₂,RN(SiH₂—CH₂—CH₂—Si(Nhexyl₂)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NCyHexyl₂)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NMeH)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NEtH)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NnPrH)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NiPrH)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NBuH)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NiBuH)₃)₂,RN(SiH₂—CH₂—CH₂—Si(NtBuH)₃)₂, RN(SiH₂—CH₂—CH₂—Si(NAmH)₃)₂,RN(SiH₂—CH₂—CH₂—Si(pyridine)₃)₂, RN(SiH₂—CH₂—CH₂—Si(pyrrole)₃)₂,RN(SiH₂—CH₂—CH₂—Si(pyrrolidine)₃)₂, andRN(SiH₂—CH₂—CH₂—Si(imidazole)₃)₂. These precursors are suitable forvapor deposition or coating applications due at least partially to thebenefits discussed above for SiH bonds The terminal amino ligands mayalso provide improved thermal stability, as discussed above, as well asan additional N and/or C source for the resulting film. Finally, thelisted precursors having lower molecular weights and higher vaporpressures are better suited for vapor deposition techniques, whereasthose having higher molecular weights are better suited for coatingtechniques.

Returning to formula (II), when t=1 and R, R², R³, R⁴ and R⁵═H, thedisclosed polycarbosilazane precursor presented contain a unit havingthe formula [—NH—SiH₂—CH₂—SiH₂—]_(n) (i.e., [—NH-DSP-]_(n)).[—NH-DSP-]_(n) contains many Si—H bonds, making it more reactive to thesubstrate surface. As a result, this precursor may be suitable for spinon deposition processes. Applicants believe that this precursor may evenbe sufficiently reactive to attach to Si—Cl or Si—OH terminated or evenSi terminated substrate surfaces in CVD or ALD processes.

When t=1; R², R³, R⁴ and R⁵═H; and R═Si_(x)H_(2x+1), with x=1 to 4, thedisclosed precursors contain a unit having the formula[—N(SiH₃)—SiH₂—CH₂—SiH₂—]_(n), [—N(Si₂H₅)—SiH₂—CH₂—SiH₂—]_(n),[—N(Si₃H₇)—SiH₂—CH₂—SiH₂—]_(n), [—N(Si₄H₉)—SiH₂—CH₂—SiH₂—]_(n). Thechoice of silyl ligand may help provide a film having the desiredsilicon content. In other words, the Si₄H₉ ligand may produce a filmwith more Si than that produced by the SiH₃ ligand.

When t=1; R², R³, R⁴ and R⁵═H; and R═SiH_(z)(C_(y)H_(2y+1))_(3-z), withy=1 to 6, z=0 to 2, the disclosed precursors contain a unit having theformula including, but not limited to, [—N(Si(Me)₃)-SiH₂—CH₂—SiH₂—]_(n),[—N(Si(Et)₃)-SiH₂—CH₂—SiH₂—]_(n), [—N(Si(iPr)₃)-SiH₂—CH₂—SiH₂—]_(n),[—N(Si(nPr)₃)-SiH₂—CH₂—SiH₂—]_(n), [—N(Si(Bu)₃)-SiH₂—CH₂—SiH₂—]_(n),[—N(Si(iBu)₃)-SiH₂—CH₂—SiH₂—]_(n), [—N(Si(tBu)₃)-SiH₂—CH₂—SiH₂—]_(n),[—N(Si(amyl)₃)-SiH₂—CH₂—SiH₂—]_(n), [—N(Si(hexyl)₃)-SiH₂—CH₂—SiH₂—]_(n),[—Nx(SiH(Me)₂)-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH(Et)₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH(iPr)₂)-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH(nPr)₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH(Bu)₂)-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH(iBu)₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH(tBu)₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH(amyl)₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH(hexyl)₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(Me))-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH₂(Et))-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(iPr))-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH₂(nPr))-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(Bu))-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH₂(iBu))-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(tBu))-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH₂(amyl))-SiH₂—CH₂—SiH₂—]_(n),and [—N(SiH₂(hexyl))-SiH₂—CH₂—SiH₂—]_(n).

When t=1; R², R³, R⁴ and R⁵═H; and R=aR^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group, with b=1 to 2 andR^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) are independently H or aC₁-C₆ hydrocarbon group, the disclosed precursors contain a unit havingthe formula including, but not limited to,[—N(SiH₃—CH₂—SiH₂)—SiH₂—CH₂—SiH₂—]_(n),[—N(SiH₃—CH₂—CH₂—SiH₂)—SiH₂—CH₂—SiH₂—]_(n),[—N(SiMe₃-CH₂—SiMe₂)-SiH₂—CH₂—SH₂—]_(n),[—N(SiMe₃-CH₂—CH₂—SiMe₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiEt₃-CH₂—SiEt₂)-SiH₂—CH₂—SiH₂—]_(n), and[—N(SiEt₃-CH₂—CH₂—SiEt₂)-SiH₂—CH₂—SiH₂—]_(n).

When t=1; R², R³, R⁴ and R⁵═H; and R═C_(y)H_(2y+1), with y=1 to 6, thedisclosed polycarbosilazane precursors contain a unit having the formulaincluding, but not limited to, [—N(Me)-SiH₂—CH₂—SiH₂—]_(n),[—N(Et)-SiH₂—CH₂—SiH₂—]_(n), [—N(iPr)-SiH₂—CH₂—SiH₂—]_(n),[—N(nPr)-SiH₂—CH₂—SiH₂—]_(n), [—N(Bu)-SiH₂—CH₂—SiH₂—]_(n),[—N(iBu)-SiH₂—CH₂—SiH₂—]_(n), [—N(tBu)-SiH₂—CH₂—SiH₂—]_(n),[—N(amyl)-SiH₂—CH₂—SiH₂—]_(n), and [—N(hexyl)-SiH₂—CH₂—SiH₂—]_(n). Thisfamily of compounds may be useful for deposition of films having carboncontent, such as SiOC or SiNC, because the Si—C bond (for Si—R) is nothighly reactive and is likely to remain intact during the depositionprocess. As a result, to prevent deposition of too much C, y ispreferably 1 to 3. These precursors are also easier to synthesize thanthe [—NH-DSP-]_(n) analogs because the RNHR₂ reactant is a liquid forEt, Pr, Bu, Pentyl, and Hexyl.

When t=1; R², R³, R⁴ and R⁵═H; andR═R^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) with b=1 to 2 and R^(1′),R^(2′), R^(3′), R^(4′) and R^(5′)═H, the disclosed polycarbosilazaneprecursor contain a unit having the formula including, but not limitedto, [—N(—SiH₂—CH₂—SiH₃)—SiH₂—CH₂—SiH₂—]_(n) (i.e., [—N(DSP)-DSP-]_(n))or [—N(—SiH₂—CH₂—CH₂—SiH₃)—SiH₂—CH₂—SiH₂—]_(n) (i.e.,[—N(DSB)-DSP-]_(n)).

When t=1; R², R³, R⁴ and R⁵═H; and R═SiH_(x)(NR′R″)_(3-x) with x=1 or 2and R′ and R″ independently Me, Et, iPr, nPr, the disclosedcarbosilazane precursors contain a unit having the formula including,but not limited to, [—N(SiH₂NMe₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH₂NEt₂)-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH₂NiPr₂)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH₂NnPr₂)-SiH₂—CH₂—SiH₂—]_(n), [—N(SiH₂NMeEt)-SiH₂—CH₂—SiH₂—]_(n),[—N(SiH(NMe₂)₂)-SiH₂—CH₂—SiH₂—]_(n), and[—N(SiH(NEt₂)₂)-SiH₂—CH₂—SiH₂—]_(n).

Exemplary polycarbosilazane precursors presented in formula (II) whereint=1 and R, R³, R⁴ and R⁵═H contain a unit having the formula including,but not limited to, [—NH—H₂Si—CH₂—SiH(CH₂═CH₂)—]_(n),[—NH—H₂Si—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n), [—NH—H₂Si—CH₂—SiH(NH₂)—]_(n),[—NH—H₂Si—CH₂—SiH(NMe₂)-]_(n), [—NH—H₂Si—CH₂—SiH(NMeEt)-]_(n),[—NH—H₂Si—CH₂—SiH(NEt₂)-]_(n), [—NH—H₂Si—CH₂—SiH(NnPr₂)—]_(n),[—NH—H₂Si—CH₂—SiH(NiPr₂)—]_(n), [—NH—H₂Si—CH₂—SiH(NBu₂)-]_(n),[—NH—H₂Si—CH₂—SiH(NiBu₂)-]_(n), [—NH—H₂Si—CH₂—SiH(NtBu₂)-]_(n),[—NH—H₂Si—CH₂—SiH(NAm₂)-]_(n), [—NH—H₂Si—CH₂—SiH(NCyPentyl₂)-]_(n),[—NH—H₂Si—CH₂—SiH(Nhexyl₂)-]_(n), [—NH—H₂Si—CH₂—SiH(NCyHexyl₂)-]_(n),[—NH—H₂Si—CH₂—SiH(NMeH)—]_(n), [—NH—H₂Si—CH₂—SiH(NEtH)—]_(n),[—NH—H₂Si—CH₂—SiH(NnPrH)—]_(n), [—NH—H₂Si—CH₂—SiH(NiPrH)—]_(n),[—NH—H₂Si—CH₂—SiH(NBuH)—]_(n), [—NH—H₂Si—CH₂—SiH(NiBuH)—]_(n),[—NH—H₂Si—CH₂—SiH(NtBuH)—]_(n), [—NH—H₂Si—CH₂—SiH(NAmH)—]_(n),[—NH—H₂Si—CH₂—SiH(pyridine)-]_(n), [—NH—H₂Si—CH₂—SiH(pyrrole)-]_(n),[—NH—H₂Si—CH₂—SiH(pyrrolidine)-]_(n), and[—NH—H₂Si—CH₂—SiH(imidazole)-]_(n). These precursors are suitable forspin-coating applications due at least partially to the benefitsdiscussed above for SiH bonds. The amino ligand may also provideimproved thermal stability, as discussed above, as well as an additionalN and/or C source for the resulting film.

Exemplary polycarbosilazane precursors presented in formula (II) whereint=1 and R, R⁴ and R⁵═H contain a unit having the formula including, butnot limited to, [—NH—H₂Si—CH₂—Si—(CH₂═CH₂)₂—]_(n),[—NH—H₂Si—CH₂—Si—(CH₂—CH₂═CH₂)₂—]_(n), [—NH—H₂Si—CH₂—Si(NH₂)₂—]_(n),[—NH—H₂Si—CH₂—Si(NMe₂)₂—]_(n), [—NH—H₂Si—CH₂—Si(NMeEt)₂-]_(n),[—NH—H₂Si—CH₂—Si(NEt₂)₂—]_(n), [—NH—H₂Si—CH₂—Si(NnPr₂)₂-]_(n),[—NH—H₂Si—CH₂—Si(NiPr₂)₂-]_(n), [—NH—H₂Si—CH₂—Si(NBu₂)₂-]_(n),[—NH—H₂Si—CH₂—Si(NiBu₂)₂-]_(n), [—NH—H₂Si—CH₂—Si(NtBU₂)₂-]_(n),[—NH—H₂Si—CH₂—Si(NAM₂)₂-]_(n), [—NH—H₂Si—CH₂—Si(NCyPentyl₂)₂-]_(n),[—NH—H₂Si—CH₂—Si(Nhexyl₂)₂-]_(n), [—NH—H₂Si—CH₂—Si(NCyHexyl₂)₂-]_(n),[—NH—H₂Si—CH₂—Si(NMeH)₂-]_(n), [—NH—H₂Si—CH₂—Si(NEtH)₂—]_(n),[—NH—H₂Si—CH₂—Si(NnPrH)₂—]_(n), [—NH—H₂Si—CH₂—Si(NiPrH)₂—]_(n),[—NH—H₂Si—CH₂—Si(NBuH)₂—]_(n), [—NH—H₂Si—CH₂—Si(NiBuH)₂—]_(n),[—NH—H₂Si—CH₂—Si(NtBuH)₂—]_(n), [—NH—H₂Si—CH₂—Si(NAmH)₂—]_(n),[—NH—H₂Si—CH₂—Si(pyridine)₂-]_(n), [—NH—H₂Si—CH₂—Si(pyrrole)₂-]_(n),[—NH—H₂Si—CH₂—Si(pyrrolidine)₂-]_(n), and[—NH—H₂Si—CH₂—Si(imidazole)₂-]_(n). These precursors are suitable forspin-coating applications due at least partially to the benefitsdiscussed above for SiH bonds The terminal amino ligand may also provideimproved thermal stability, as discussed above, as well as an additionalN and/or C source for the resulting film.

Exemplary polycarbosilazane precursors presented in formula (II) whereint=1 and R, R³ and R⁵═H contain a unit having the formula including, butnot limited to, [—NH—SiH(CH₂═CH₂)—CH₂—SiH(CH₂═CH₂)—]_(n),[—NH—SiH(CH₂—CH₂═CH₂)—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n),[—NH—SiH(NH₂)—CH₂—SiH(NH₂)—]_(n), [—NH—SiH(NMe₂)—CH₂—SiH(NMe₂)-]_(n),[—NH—SiH(NMeEt)-CH₂—SiH(NMeEt)-]_(n),[—NH—SiH(NEt₂)-CH₂—SiH(NEt₂)-]_(n),[—NH—SiH(NnPr₂)-CH₂—SiH(NnPr₂)-]_(n),[—NH—SiH(NiPr₂)-CH₂—SiH(NiPr₂)-]_(n),[—NH—SiH(NBu₂)-CH₂—SiH(NBu₂)-]_(n),[—NH—SiH(NiBu₂)-CH₂—SiH(NiBu₂)-]_(n),[—NH—SiH(NtBu₂)-CH₂—SiH(NtBu₂)-]_(n),[—NH—SiH(NAm₂)-CH₂—SiH(NAm₂)-]_(n),[—NH—SiH(NCyPentyl₂)-CH₂—SiH(NCyPentyl₂)-]_(n),[—NH—SiH(Nhexyl₂)-CH₂—SiH(Nhexyl₂)-]_(n),[—NH—SiH(NCyHexyl₂)-CH₂—SiH(NCyHexyl₂)-]_(n),[—NH—SiH(NMeH)—CH₂—SiH(NMeH)—]_(n), [—NH—SiH(NEtH)—CH₂—SiH(NEtH)—]_(n),[—NH—SiH(NnPrH)—CH₂—SiH(NnPrH)—]_(n),[—NH—SiH(NiPrH)—CH₂—SiH(NiPrH)—]_(n),[—NH—SiH(NBuH)—CH₂—SiH(NBuH)—]_(n),[—NH—SiH(NiBuH)—CH₂—SiH(NiBuH)—]_(n),[—NH—SiH(NtBuH)—CH₂—SiH(NtBuH)—]_(n),[—NH—SiH(NAmH)—CH₂—SiH(NAmH)—]_(n),[—NH—SiH(pyridine)-CH₂—SiH(pyridine)-]_(n),[—NH—SiH(pyrrole)-CH₂—SiH(pyrrole)-]_(n),[—NH—SiH(pyrrolidine)-CH₂—SiH(pyrrolidine)-]_(n), and[—NH—SiH(imidazole)-CH₂—SiH(imidazole)-]_(n). These precursors aresuitable for spin-coating applications due at least partially to thebenefits discussed above for SiH bonds The terminal amino ligand mayalso provide improved thermal stability, as discussed above, as well asan additional N and/or C source for the resulting film.

When t=2 and R, R², R³, R⁴ and R⁵═H, the disclosed polycarbosilazaneprecursor contain a unit having the formula [—NH—SiH₂—CH₂—CH₂—SiH₂—],(i.e., [—NH-DSB-]_(n)). [—NH-DSB-]_(n) contains many Si—H bonds, makingit more reactive to the substrate surface. As a result, this precursormay be suitable for spin on deposition processes. Applicants believethat this precursor may even be sufficiently reactive to attach to Si—Clterminated or even Si terminated substrate surfaces.

When t=2; R², R³, R⁴ and R⁵═H; and R═Si_(x)H_(2x+1), with x=1 to 4, thedisclosed polycarbosilazane precursors contain a unit having the formula[—N(SiH₃)—SiH₂—CH₂—CH₂—SiH₂—]_(n), [—N(Si₂H₅)—SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si₃H₇)—SiH₂—CH₂—CH₂—SiH₂—]_(n), and/or[—N(Si₄H₉)—SiH₂—CH₂—CH₂—SiH₂—]_(n). The choice of silyl ligand may helpprovide a film having the desired silicon content. In other words, theSi₄H₉ ligand may produce a film with more Si than that produced by theSiH₃ ligand.

When t=2; R¹, R², R³, R⁴ and R⁵═H; and R═SiH_(z)(C_(y)H_(2y+1))_(3-z),with y=1 to 6 and z=0 to 2, the disclosed carbosilazane precursorcontain a unit having the formula including, but not limited to,[—N(Si(Me)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(Et₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(iPr)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(nPr)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(Bu)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(iBu)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(tBu)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(amyl)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Si(hexyl)₃)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—Nx(SiH(Me)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(Et)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(iPr)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(nPr)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(Bu)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(iBu)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(tBu)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(amyl)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH(hexyl)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(Me))-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(Et))-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(iPr))-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(nPr))-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(Bu))-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(iBU))-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂(tBu))-SiH₂—CH₂—CH₂—SiH₂—]_(n), and[—N(SiH₂(amyl))-SiH₂—CH₂—CH₂—SiH₂—]_(n), and[—N(SiH₂(hexyl))-SiH₂—CH₂—CH₂—SiH₂—]_(n).

When t=2, R═C_(y)H_(2y+1) (y=1 to 6), and R², R³, R⁴ and R⁵═H, thedisclosed polycarbosilazane precursors contain a unit having the formulaincluding, but not limited to, [—N(Me)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(Et)-SiH₂—CH₂—CH₂—SiH₂—]_(n), [—N(iPr)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(nPr)-SiH₂—CH₂—CH₂—SiH₂—]_(n), [—N(Bu)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(iBu)-SiH₂—CH₂—CH₂—SiH₂—]_(n), [—N(tBu)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(amyl)-SiH₂—CH₂—CH₂—SiH₂—]_(n), and[—N(hexyl)-SiH₂—CH₂—CH₂—SiH₂—]_(n). This family of compounds may beuseful for deposition of films having carbon content, such as SiOC orSiNC, because the Si—C bond (for Si—R) is not highly reactive and islikely to remain intact during the deposition process. As a result, toprevent deposition of too much C, y is preferably 1 to 3. Theseprecursors are also easier to synthesize than the [—NH-DSB-]_(n) analogsbecause the RNHR₂ reactant is a liquid for Et, Pr, Bu, Pentyl, andHexyl.

When t=2; R², R³, R⁴ and R⁵═H; and R=aR^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group, with b=1 to 2 andR^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) independently H or a C₁-C₆hydrocarbon group, the disclosed polycarbosilazane precursors contain aunit having the formula including, but not limited,[—N(SiH₃—CH₂—SiH₂)—SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₃—CH₂—CH₂—SiH₂)—SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiMe₃-CH₂—SiMe₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiMe₃-CH₂—CH₂—SiMe₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiEt₃-CH₂—SiEt₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n), and[—N(SiEt₃-CH₂—CH₂—SiEt₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n).

When t=2; R², R³, R⁴ and R⁵═H; andR═R^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) with b=1 to 2 and R^(1′),R^(2′), R^(3′), R^(4′) and R^(5′)═H, the disclosed polycarbosilazaneprecursor contain a unit having the formula[—N(—SiH₂—CH₂—SiH₃)—SiH₂—CH₂—CH₂—SiH₂—]_(n) (i.e., [—N(DSP)-DSB-]_(n))or [—N(—SiH₂—CH₂—CH₂—SiH₃)—SiH₂—CH₂—CH₂—SiH₂—]_(n) (i.e.,[—N(DSB)-DSB-]_(n)). [—N(DSP)-DSB-]_(n) and [—N(DSB)-DSB-]_(n) containsmany Si—H bonds, making it more reactive to the substrate surface. As aresult, this precursor may be suitable for spin on deposition processes.Applicants believe that this precursor may even be sufficiently reactiveto attach to Si—Cl terminated or even Si terminated substrate surfaces.

When t=2; R², R³, R⁴ and R⁵═H; and R═SiH_(x)(NR′R″)_(3-x) with x=1 or 2and R′ and R″ independently are Me, Et, iPr, nPr, the disclosedcarbosilazane precursors contain a unit having the formula including,but not limited to, [—N(SiH₂NMe₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂NEt₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂NiPr₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂NnPr₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n),[—N(SiH₂NMeEt)-SiH₂—CH₂CH₂—SiH₂—]_(n),[—N(SiH(NMe₂)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n), and[—N(SiH(NEt₂)₂)-SiH₂—CH₂—CH₂—SiH₂—]_(n).

Exemplary polycarbosilazane precursors presented in formula (II) whereint=2 and R, R³, R⁴ and R⁵═H contain a unit having the formula including,but not limited to, [—NH—H₂Si—CH₂—CH₂—SiH(CH₂═CH₂)—]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NH₂)—]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NMe₂)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NMeEt)-]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NEt₂)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NnPr₂)—]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NiPr₂)—]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NBu₂)-]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NiBu₂)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NtBu₂)-]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NAm₂)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NCyPentyl₂)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(Nhexyl₂)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NCyHexyl₂)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NMeH)—]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NEtH)—]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NnPrH)—]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NiPrH)—]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NBuH)—]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NiBuH)—]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(NtBuH)—]_(n), [—NH—H₂Si—CH₂—CH₂—SiH(NAmH)—]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(pyridine)-]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(pyrrole]_(n),[—NH—H₂Si—CH₂—CH₂—SiH(pyrrolidine)-]_(n), and[—NH—H₂Si—CH₂—CH₂—SiH(imidazole)-]_(n). These precursors are suitablefor spin-coating applications due at least partially to the benefitsdiscussed above for SiH bonds The amino ligand may also provide improvedthermal stability, as discussed above, as well as an additional N and/orC source for the resulting film.

Exemplary polycarbosilazane precursors presented in formula (II) whereint=2 and R, R⁴ and R⁵═H contain a unit having the formula including, butnot limited to, [—NH—H₂Si—CH₂—CH₂—Si—(CH₂═CH₂)₂—]_(n),[—NH—H₂Si—CH₂—CH₂—Si—(CH₂—CH₂═CH₂)₂—]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NH₂)₂]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NMe₂)₂—]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NMeEt)₂—]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NEt₂)₂]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NnPr₂)₂-]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NiPr₂)₂]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NBu₂)₂-]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NiBu₂)₂-]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NtBu₂)₂-]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NAm₂)₂-]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NCyPentyl₂)₂-]_(n),[—NH—H₂Si—CH₂—CH₂—Si(Nhexyl₂)₂-]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NCyHexyl₂)₂-]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NMeH)₂—]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NEtH)₂—]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NnPrH)₂—]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NiPrH)₂—]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NBuH)₂—]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NiBuH)₂—]_(n),[—NH—H₂Si—CH₂—CH₂—Si(NtBuH)₂—]_(n), [—NH—H₂Si—CH₂—CH₂—Si(NAmH)₂—]_(n),[—NH—H₂Si—CH₂—CH₂—Si(pyridine)₂-]_(n),[—NH—H₂Si—CH₂—CH₂—Si(pyrrole)₂-]_(n),[—NH—H₂Si—CH₂—CH₂—Si(pyrrolidine)₂-]_(n), and[—NH—H₂Si—CH₂—CH₂—Si(imidazole)₂-]_(n). These precursors are suitablefor spin-coating applications due at least partially to the benefitsdiscussed above for SiH bonds The amino ligand may also provide improvedthermal stability, as discussed above, as well as an additional N and/orC source for the resulting film.

Exemplary polycarbosilazane precursors presented in formula (II) whereint=2 and R, R³ and R⁵═H contain a unit having the formula including, butnot limited to, [—NH—SiH(CH₂═CH₂)—CH₂—CH₂—SiH(CH₂═CH₂)]_(n),[—NH—SiH(CH₂—CH₂═CH₂)—CH₂—CH₂—SiH(CH₂—CH₂═CH₂)—]_(n),[—NH—SiH(NH₂)—CH₂—CH₂—SiH(NH₂)—]_(n),[—NH—SiH(NMe₂)-CH₂—CH₂—SiH(NMe₂)-]_(n),[—NH—SiH(NMeEt)-CH₂—CH₂—SiH(NMeEt)-]_(n),[—NH—SiH(NEt₂)-CH₂—CH₂—SiH(NEt₂)-]_(n),[—NH—SiH(NnPr₂)-CH₂—CH₂—SiH(NnPr₂)-]_(n),[—NH—SiH(NiPr₂)-CH₂—CH₂—SiH(NiPr₂)-]_(n),[—NH—SiH(NBu₂)-CH₂—CH₂—SiH(NBu₂)-]_(n),[—NH—SiH(NiBu₂)-CH₂—CH₂—SiH(NiBu₂)-]_(n),[—NH—SiH(NtBu₂)-CH₂—CH₂—SiH(NtBu₂)-]_(n),[—NH—SiH(NAm₂)-CH₂—CH₂—SiH(NAm₂)-]_(n),[—NH—SiH(NCyPentyl₂)-CH₂—CH₂—SiH(NCyPentyl₂)-]_(n),[—NH—SiH(Nhexyl₂)-CH₂—CH₂—SiH(Nhexyl₂)-]_(n),[—NH—SiH(NCyHexyl₂)-CH₂—CH₂—SiH(NCyHexyl₂)-]_(n),[—NH—SiH(NMeH)—CH₂—CH₂—SiH(NMeH)—]_(n),[—NH—SiH(NEtH)—CH₂—CH₂—SiH(NEtH)—]_(n),[—NH—SiH(NnPrH)—CH₂—CH₂—SiH(NnPrH)—]_(n),[—NH—SiH(NiPrH)—CH₂—CH₂—SiH(NiPrH)—]_(n),[—NH—SiH(NBuH)—CH₂—CH₂—SiH(NBuH)—]_(n),[—NH—SiH(NiBuH)—CH₂—CH₂—SiH(NiBuH)—]_(n),[—NH—SiH(NtBuH)—CH₂—CH₂—SiH(NtBuH)—]_(n),[—NH—SiH(NAmH)—CH₂—CH₂—SiH(NAmH)—]_(n),[—NH—SiH(pyridine)-CH₂—CH₂—SiH(pyridine)-]_(n),[—NH—SiH(pyrrole)-CH₂—CH₂—SiH(pyrrole]_(n),[—NH—SiH(pyrrolidine)-CH₂—CH₂—SiH(pyrrolidine)-]_(n), and[—NH—SiH(imidazole)-CH₂—CH₂—SiH(imidazole)-]_(n). These precursors aresuitable for spin-coating applications due at least partially to thebenefits discussed above for SiH bonds The amino ligand may also provideimproved thermal stability, as discussed above, as well as an additionalN and/or C source for the resulting film.

In one exemplary synthesis method, the disclosed precursors may besynthesized using a halogen-containing reactant. In a second exemplarysynthesis method, a halogen-containing reactant is not required. Both ofthe disclosed synthesis methods may provide high yield. The disclosedsynthesis methods may be more selective than conventional synthesismethods (i.e., may yield more of the desired precursor than prior artmethods). The halogen free synthesis method may be useful to produceprecursors used with substrates sensitive to halides.

Applicants have discovered that specific solvent polarity selection aidsin reducing the synthesis of undesired by-products. For example, in anon-polar solvent, RN(R⁴R⁵Si—(CH₂)_(m)SiR¹R²R³)₂ may be selectivelyproduced with minimal production of N(R⁴R⁵Si—(CH₂)_(m)SiR¹R²R³)₃by-product. Conversely, in a polar solvent, N(R⁴R⁵Si—(CH₂)_(m)SiR¹R²R³)₃containing compounds may be selectively produced with minimalRN(R⁴R⁵Si—(CH₂)_(m)SiR¹R²R³)₂ by-product.

The disclosed synthesis methods may be scaled up to produce large amountof the product. For example, scaled up to approximately 1 kg toapproximately 100 kg.

In the exemplary halogen-free synthesis route, a starting reagent havingthe formula H₃Si—(CH₂)SiH₃ (i.e., DSP), is reacted with ammonia in apressure reactor in the presence of transitional metal basedheterogeneous or homogeneous catalysts. The reaction may be neat orutilize a solvent. Exemplary catalysts include, but are not limited to,Ru, Pt, Pd. If a solvent is used, the solvent may be selected fromhydrocarbons, amines, ethers, among others. This reaction may produce amixture of the di-substituted and tri-substituted product (e.g., HNDSP2and NDSP3), or a linear or branched oligomer of N-DSP (i.e., a precursorcontaining a unit having the formula [—NR-DSP-]_(n), wherein R isdefined above). The reaction parameters may be optimized to produce thedesired precursors. Exemplary reaction parameters include reactiontemperature, stoichiometry and reaction time.

Replacing the DSP starting reagent above with a DSB starting reagentyields HNDSB2 or NDSB3. The reaction formula are as follows.H₃Si—CH₂—CH₂—SiH₃+NH₃→HNDSB2; H₃Si—CH₂—CH₂—SiH₃+NH₃→NDSB3

N-DSB-containing oligomers [—NH-DSB], and [—N(DSB)-DSB-]_(n) (n=2 to400) may be synthesized via the halogen free route by replacing DSP withDSB in a pressure reactor in the presence of transition metals basedheterogeneous catalysts like but not limited to Ru, Pt, Pd andtransition metals based homogeneous catalysts and heating the mixture at20-150° C. H₃Si—CH₂—CH₂—SiH₃+NH₃→HN(DSB)₂→[—NH-DSB-]_(n);H₃Si—CH₂—CH₂—SiH₃+NH₃→N(DSB)₃→[—N(DSB)-DSB-]_(n).

The starting DSP or DSB reagents may be synthesized by reacting LiAlH₄(LAH) with SiCl₃CH₂—SiCl₃ in diglyme (H₃COC₂H₄OC₂H₄OCH₃) orSiCl₃CH₂CH₂SiCl₃ in di-n-butyl ether (H₉C₄OC₄H₉). 3LiAlH₄+2SiCl₃CH₂SiCl₃_(→) 2DSP+3LiAlCl₄or 3LiAlH₄+2SiCl₃CH₂CH₂SiCl₃→2DSB+3LiAlCl₄.

Alternatively, the ammonia reactant may be replaced with an amine havingthe formula R—NH₂, with R being a C₁-C₆ linear, branched, saturated orunsaturated hydrocarbon. This halogen-free reaction produces (-DSP-NR—)or (-DSB-NR—).

RN(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂ may be formed in a pressure reactor by mixingHN(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂ with a carbosilane (e.g., H₃SiC_(n)H_(2n)SiH₃)or corresponding R-containing compounds, with or without a solvent, inthe presence of transitional metal based heterogeneous or homogeneouscatalysts. Exemplary catalysts include but are not limited to Ru, Pt,Pd. The mixture is heated to a temperature ranging between 20-150° C.The reaction yields a combination of RNDSP2, NDSP3 and N-DSP-containingoligomers. Pure RNDSP2, NDSP3 or N-DSP-containing oligomer may beobtained by proper distillation or isolation methods. For example,(H₃Si—CH₂—SiH₂—)₂—N—SiH₂—C_(n)H_(2n)—SiH₃ may be synthesized in apressure reactor by reacting HN(DSP)₂ with carbosilaneH₃SiC_(n)H_(2n)SiH₃ in the presence of a catalyst, such as Ru/C, Pt/C,Pd/C.

HN(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂ may be reacted with a silane having theformula Si_(x)R′_(2x+2) (x=1-4) to produce[Si_(x)R′_(2x+1)]—N(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂. More particularly, HNDSP2reacts with SiH₄ to produce (SiH₃)N(DSP)₂. The dehydrogenative couplingreaction (halogen free route) occurs in a pressure reactor in thepresence of a transition metal based heterogeneous catalyst, such as Ru,Pt, Pd and transition metals based homogeneous catalysts. The synthesismay take place with or without a solvent. The mixture is heated to atemperature between 20-150° C. HN(DSP)₂+Si_(n)H_(2n+2)→RN(DSP)₂,R═Si_(n)H_(2n+1); n=1 to 4. When n=1, (DSP)-N(SiH₃)-(DSP) may also beproduced. When n=2, (DSP)-N(Si₂H₅)-(DSP) may also be produced.

In another example, HN(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂ may be reacted with acarbosilane having the formula SiH₃C_(x)H_(2x+1) (x=1-4) to produce(SiH₂C_(x)H_(2x+1))N(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂. More particularly, HN(DSP)₂reacts with SiH₃Me to produce (MeSiH₂)N(DSP)₂.

(DSP)₂N—(SiH₂(CH₂)_(n)SiH₃) or (DSB)₂N—(SiH₂(CH₂),SiH₃), wherein n=1 to2, may be synthesized by reacting HN(DSP)₂ or HN(DSB)₂ with(H₃SiC_(n)H_(2n)SiH₃) (n=1 to 2) in a pressure reactor bydehydrogenative coupling (halogen free route) in the presence of acatalyst like Ru/C, Pt/C, Pd/C, having the reaction formula: (DSP)₂N—HH₃SiC_(n)H_(2n)SiH₃=(DSP)₂N—SiH₂C_(n)H_(2n)SiH₃+H₂, wherein n=1 to 2.

Alternatively, the RNDSP2 or RNDSB2 product may be synthesized via ahalogenated route. HNDSP2 is mixed with the corresponding halogenatedalkane, silane, or carbosilanes in a solvent. Suitable solvents includehydrocarbons or ethereal solvents like diethyether, tetrahydrofuran(THF), glymes or anisole. Since, HCl is a byproduct of this reaction, aHCl scavenger is required. Exemplary HCl scavengers include any amine,but preferably a tertiary amine. For example,(H₃Si—CH₂—SiH₂—)₂—N—SiH₂—C_(n)H_(2n)—SiH₃ (n=1 to 2) may be synthesizedby reacting HN(DSP)₂ or HN(DSB)₂ and the corresponding halogenatedcarbosilane (X—H₂SiC_(n)H_(2n)SiH₃; X═Cl, Br, I, n=1 to 2) with orwithout a solvent. Exemplary solvents include hydrocarbons or aromaticsolvents like benzene, toluene, tertiary amine etc.

HN(—SiR₄R₅—CH₂—SiR¹R²R³)₂ or N(—SiR⁴R⁵—CH₂—SiR¹R²R³)₃ may be selectivelysynthesized by mixing X—N(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂ and NH₃ in a solvent.If a non-polar solvent is used, such as toluene,HN(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂ is produced. If a polar solvent is used,N(—SiR⁴R⁵—CH₂—SiR¹R²R³)₃ is produced. Exemplary but non-limiting polarsolvents include ethereal solvents such as diethyether, THF, glymes oranisole. For example, NDSP3 may be selectively synthesized by mixingDSP-Cl and ammonia in an ethereal solvent. Alternatively, HNDSP2 may beselectively synthesized by mixing DSP-Cl and ammonia in toluene. SinceHCl is the byproduct of these reactions, a HCl scavenger is required.Exemplary HCl scavengers include but are not limited to amines andpreferably a tertiary amine or excess of ammonia depending on thedesired product.

HN(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂ may be reacted with a halogenated alkanehaving the formula R—X, with X being Cl, Br, or I and R═C_(x)H_(2x+2),to produce (C_(x)H_(2x+1))N(—SiR⁴R⁵—CH₂—SiR¹R²R³)₂. For example,HN(DSP)₂ reacts with CH₃Cl to produce (Me)N(DSP)₂.

(SiH₂NMe₂)N(DSP)₂, may be synthesized by reacting HN(DSP)₂ andX—SiH₂NMe₂ with or without a solvent. The solvent may be a hydrocarbonsolvent, tertiary amine, etc.

(DSP)₂N—(SiH₂(CH₂)_(n)SiH₃) or (DSB)₂N—(SiH₂(CH₂)_(n)SiH₃) may besynthesized by reacting HN(DSP)₂ or HN(DSB)₂ with the correspondinghalogenated carbosilane (X—H₂SiC_(n)H_(2n)SiH₃; X═Cl, Br, I) with orwithout a solvent. Exemplary non-limiting solvents include hydrocarbonsolvents, aromatic solvents like benzene, toluene etc, tertiary amineetc.

RNDSP2 or RNDSB2 may be synthesized by mixing HNDSP2 with nBuLi (analkyllithium linear or branched). The acidic proton on HNDSP2 may beextracted by reaction with nBuLi followed by mixing halogenatedcompounds having the formula of R—X, wherein X═Cl, Br or I; R is analkane, silane, carbosilane, phenyl group or silylamino group (SiNR′₂ orSiNR′R″), wherein R′ and R″ are each independently a H, a hydrocarbongroup (C1 to C12), in a hydrocarbon solvent such as, but not limited to,pentane, hexane, etc. or ethereal solvent such as, but not limited to,diethyether, THF, glymes or anisole. For example, HNDSP2 reacts withSiMe₃X to produce (SiMe₃)N(DSP)₂; HNDSP2 reacts with CH₃X to produce(Me)N(DSP)₂. (DSP)₂N—[CH₂]_(n)H, wherein n=1-6, may be synthesized byreacting HNDSP2 with nBuLi followed by alkylhalide (alkyl=C_(n)H_(2x+1)and halide=Cl, Br, I) in a hydrocarbon solvent like pentane, hexane etc.or ethereal solvent like diethylether, THF etc, aromatic solvents likebenzene, toluene etc., having the reaction formula:HNDSP2+R—X→RNDSP2+HX, wherein X═Cl, Br or I; R=n=1-6.

Alternatively, HNDSB2 and NDSB3 may also be selectively synthesized byreplacing DSP-Cl with DSB-Cl in the above halogen involved route forproducing HNDSP2 and NDSP3. ClSiH₂—CH₂—CH₂—SiH₃+NH₃→HN(DSB)₂+HCl;ClSiH₂—CH₂—CH₂—SiH₃+NH₃→NDSB3+HCl. In a non-polar solvent, HNDSB2 may beselectively produced. Replacing the non-polar solvent with a polarsolvent, NDSB3 may be selectively produced with the halogen involvedroute.

One of ordinary skill in the art will recognize that the substituted DSPand DSB reactants may be synthesized using HSiR₂—CH₂—SiR₃ orClSiR₂—CH₂—SiR₃ and the dehydrocoupling or the Cl exchange route,respectively.

To ensure process reliability, the resulting Si-containing film formingcomposition may be purified by continuous or fractional batchdistillation or sublimation prior to use to a purity ranging fromapproximately 90% w/w to approximately 100% w/w, preferably ranging fromapproximately 99% w/w to approximately 100% w/w. The Si-containing filmforming compositions may contain any of the following impurities:undesired congeneric species; solvents; chlorinated metal compounds; orother reaction products. Preferably, the total quantity of theseimpurities is below 0.1% w/w.

The concentration of each of solvent, such as toluene, hexane,substituted hexane, pentane, substituted pentane, diethyether, THF,glymes, dimethoxy ether, or anisole in the purified material may rangefrom approximately 0% w/w to approximately 5% w/w, preferably fromapproximately 0% w/w to approximately 0.1% w/w. Solvents may be used inthe composition's synthesis. Separation of the solvents from thecomposition may be difficult if both have similar boiling points.Cooling the mixture may produce solid precursor in liquid solvent, whichmay be separated by filtration. Vacuum distillation may also be used,provided the precursor product is not heated above approximately itsdecomposition point.

In one embodiment the disclosed Si-containing film forming compositioncontains less than 5% v/v, preferably less than 1% v/v, more preferablyless than 0.1% v/v, and even more preferably less than 0.01% v/v of anyof its undesired congeneric species, reactants, or other reactionproducts. This embodiment may provide better process repeatability. Thisembodiment may be produced by distillation of the Si-containing filmforming composition. In an alternate embodiment, the disclosedSi-containing film forming compositions may contain between 5% v/v and50% v/v of the carbosilazane or polycarbosilazane precursor,particularly when the mixture provides improved process parameters orisolation of the target precursor is too difficult or expensive. Forexample, a mixture of reaction products may produce a stable, liquidmixture suitable for spin-on or vapor deposition.

The concentration of trace metals and metalloids in the Si-containingfilm forming composition may each range from approximately 0 ppbw toapproximately 500 ppbw, preferably from approximately 0 ppbw toapproximately 100 ppbw, and more preferably from approximately 0 ppbw toapproximately 10 ppbw. One of ordinary skill in the art will recognizethat extraction using a reagent, such as hydrofluoric, nitric orsulfuric acid, and analysis by atomic absorption spectroscopy, x-rayfluorescence spectroscopy, or similar analytical techniques may be usedto determine the trace metal and metalloid concentrations. One ofordinary skill in the art will further recognize that the concentrationrequired for the vapor deposition precursors may be lower than those forthe polymer precursors.

The halogen concentration in the purified Si-containing film formingcomposition may range from approximately 0 ppmw to approximately 1000ppmw, preferably from 0 ppmw to 500 ppmw, and more preferably from 0ppmw to 100 pppmw. The halogen concentration may be determined by gaschromatography atomic emission spectrometry (GC-AES) or other techniquesknown in the art. These analysis techniques provide the totalconcentration of both covalently bonded halogen-silane halogens andhalide ions. Alternatively, the halide concentration may determined byion chromatography. One of ordinary skill in the art will recognize thatthe halide concentration may be lower than the halogen concentration forthe same precursor, particularly when the precursor includes Si-halogenbonds. The halide concentrations may range from approximately 0 ppmw toapproximately 500 ppmw, preferably from approximately 0 ppmw toapproximately 250 ppmw, and more preferably from approximately 0 ppmw toapproximately 75 ppmw.

Also disclosed are methods of using the disclosed precursors of FormulaI or Formula II for vapor deposition methods. To be suitable for vapordeposition methods, the disclosed precursors should have a molecularweight ranging from approximately 150 to approximately 600, preferablyfrom approximately 200 to approximately 400. The disclosed methodsprovide for the use of the Si-containing film forming composition fordeposition of silicon-containing films. The disclosed methods may beuseful in the manufacture of semiconductor, photovoltaic, LCD-TFT, orflat panel type devices. The method includes: introducing the vapor ofthe disclosed Si-containing film forming composition into a reactorhaving a substrate disposed therein: and depositing at least part of thedisclosed carbosilazane or polycarbosilazane precursor onto thesubstrate via a deposition process to form a Si-containing layer.

The disclosed methods also provide for forming a bimetal-containinglayer on a substrate using a vapor deposition process and, moreparticularly, for deposition of SiMO_(x) films, wherein x may be 0-4 andM is Ta, Hf, Nb, Mg, Al, Sr, Y, Ba, Ca, As, Sb, Bi, Sn, Pb, Co,lanthanides (such as Er), or combinations thereof.

The disclosed methods of forming silicon-containing layers on substratesmay be useful in the manufacture of semiconductor, photovoltaic,LCD-TFT, or flat panel type devices. The disclosed Si-containing filmforming compositions may deposit Si-containing films using any vapordeposition methods known in the art. Examples of suitable vapordeposition methods include chemical vapor deposition (CVD) or atomiclayer deposition (ALD). Exemplary CVD methods include thermal CVD,plasma enhanced CVD (PECVD), pulsed CVD (PCVD), low pressure CVD(LPCVD), sub-atmospheric CVD (SACVD) or atmospheric pressure CVD(APCVD), flowable CVD (f-CVD), metal organic chemical vapor deposition(MOCVD), hot-wire CVD (HWCVD, also known as cat-CVD, in which a hot wireserves as an energy source for the deposition process), radicalsincorporated CVD, and combinations thereof. Exemplary ALD methodsinclude thermal ALD, plasma enhanced ALD (PEALD), spatial isolation ALD,hot-wire ALD (HWALD), radicals incorporated ALD, and combinationsthereof. Super critical fluid deposition may also be used. Thedeposition method is preferably ALD, spatial ALD, or PE-ALD in order toprovide suitable step coverage and film thickness control.

The vapor of the Si-containing film forming composition is introducedinto a reaction chamber containing a substrate. The temperature and thepressure within the reaction chamber and the temperature of thesubstrate are held at conditions suitable for vapor deposition of atleast part of the carbosilazane precursor onto the substrate. In otherwords, after introduction of the vaporized composition into the chamber,conditions within the chamber are such that at least part of thevaporized precursor is deposited onto the substrate to form thesilicon-containing film. A co-reactant may also be used to help information of the Si-containing layer.

The reaction chamber may be any enclosure or chamber of a device inwhich deposition methods take place, such as, without limitation, aparallel-plate type reactor, a cold-wall type reactor, a hot-wall typereactor, a single-wafer reactor, a multi-wafer reactor, or other suchtypes of deposition systems. All of these exemplary reaction chambersare capable of serving as an ALD reaction chamber. The reaction chambermay be maintained at a pressure ranging from about 0.5 mTorr to about 20Torr. In addition, the temperature within the reaction chamber may rangefrom about 20° C. to about 600° C. One of ordinary skill in the art willrecognize that the temperature may be optimized through mereexperimentation to achieve the desired result.

The temperature of the reactor may be controlled by either controllingthe temperature of the substrate holder or controlling the temperatureof the reactor wall. Devices used to heat the substrate are known in theart. The reactor wall is heated to a sufficient temperature to obtainthe desired film at a sufficient growth rate and with desired physicalstate and composition. A non-limiting exemplary temperature range towhich the reactor wall may be heated includes from approximately 20° C.to approximately 600° C. When a plasma deposition process is utilized,the deposition temperature may range from approximately 20° C. toapproximately 550° C. Alternatively, when a thermal process isperformed, the deposition temperature may range from approximately 300°C. to approximately 600° C.

Alternatively, the substrate may be heated to a sufficient temperatureto obtain the desired silicon-containing film at a sufficient growthrate and with desired physical state and composition. A non-limitingexemplary temperature range to which the substrate may be heatedincludes from 150° C. to 600° C. Preferably, the temperature of thesubstrate remains less than or equal to 500° C.

The type of substrate upon which the silicon-containing film will bedeposited will vary depending on the final use intended. A substrate isgenerally defined as the material on which a process is conducted. Thesubstrates may be any suitable substrate used in semiconductor,photovoltaic, flat panel, or LCD-TFT device manufacturing. Examples ofsuitable substrates include wafers, such as silicon, silica, glass, Ge,or GaAs wafers. The wafer may have one or more layers of differingmaterials deposited on it from a previous manufacturing step. Forexample, the wafers may include silicon layers (crystalline, amorphous,porous, etc.), silicon oxide layers, silicon nitride layers, silicon oxynitride layers, carbon doped silicon oxide (SiCOH) layers, orcombinations thereof. Additionally, the wafers may include copperlayers, tungsten layers or metal layers (e.g. platinum, palladium,nickel, rhodium, or gold). The wafers may include barrier layers, suchas manganese, manganese oxide, tantalum, tantalum nitride, etc. Plasticlayers, such as poly(3,4-ethylenedioxythiophene)poly(styrenesulfonate)[PEDOT:PSS] may also be used. The layers may be planar or patterned. Insome embodiments, the substrate may be a patterened photoresist filmmade of hydrogenated carbon, for example CH_(x), wherein x is greaterthan zero (e.g., x≤4). In some embodiments, the substrate may includelayers of oxides which are used as dielectric materials in MIM, DRAM, orFeRam technologies (for example, ZrO₂ based materials, HfO₂ basedmaterials, TiO₂ based materials, rare earth oxide based materials,ternary oxide based materials, etc.) or from nitride-based films (forexample, TaN) that are used as an oxygen barrier between copper and thelow-k layer. The disclosed processes may deposit the silicon-containinglayer directly on the wafer or directly on one or more than one (whenpatterned layers form the substrate) of the layers on top of the wafer.Furthermore, one of ordinary skill in the art will recognize that theterms “film” or “layer” used herein refer to a thickness of somematerial laid on or spread over a surface and that the surface may be atrench or a line. Throughout the specification and claims, the wafer andany associated layers thereon are referred to as substrates. The actualsubstrate utilized may also depend upon the specific precursorembodiment utilized. In many instances though, the preferred substrateutilized will be selected from hydrogenated carbon, TiN, SRO, Ru, and Sitype substrates, such as polysilicon or crystalline silicon substrates.

The substrate may be patterned to include vias or trenches having highaspect ratios. For example, a conformal Si-containing film, such asSiO₂, may be deposited using any ALD technique on a through silicon via(TSV) having an aspect ratio ranging from approximately 20:1 toapproximately 100:1. In another example, trenches can be filled withpolysilazane or polycarbosilazane by flowable CVD and converted to ahard film by annealing or UV curing. The film may be converted to asilicon oxide containing film if annealed or UV cured under oxidizingatmosphere. Alternativley, the film may be converted into a siliconnitride or silicon carbonitride containing film if annealed or UV curedunder inert, nitridizing atmosphere (NH₃, hydrazine, amine, NO) orcarbonizing atmosphere.

The Si-containing film forming compositions may be supplied neat.Alternatively, the Si-containing film forming compositions may furthercomprise a solvent suitable for vapor deposition. The solvent may beselected from, among others, C₁-C₁₆ saturated or unsaturatedhydrocarbons, tetrahydrofuran (THF), dimethyl oxalate (DMO), ether,pyridine, methyl isobutyl ketone, cyclohexanone, ethanol, isopropanol,or combinations thereof.

For vapor deposition, the Si-containing film forming compositions areintroduced into a reactor in vapor form by conventional means, such astubing and/or flow meters. The composition in vapor form may be producedby vaporizing the composition through a conventional vaporization stepsuch as direct vaporization, distillation, by bubbling, or by using asublimator such as the one disclosed in PCT Publication WO2009/087609 toXu et al. The composition may be fed in liquid state to a vaporizerwhere it is vaporized before it is introduced into the reactor.Alternatively, the composition may be vaporized by passing a carrier gasinto a container containing the precursor or by bubbling the carrier gasinto the precursor. The carrier gas may include, but is not limited to,Ar, He, or N₂, and mixtures thereof. Bubbling with a carrier gas mayalso remove any dissolved oxygen present in the composition. The carriergas and precursor are then introduced into the reactor as a vapor.

If necessary, the container may be heated to a temperature that permitsthe Si-containing film forming composition to be in its liquid phase andto have a sufficient vapor pressure. The container may be maintained attemperatures in the range of, for example, 0-150° C. Those skilled inthe art recognize that the temperature of the container may be adjustedin a known manner to control the amount of Si-containing film formingcomposition vaporized.

In addition to the disclosed composition, a reaction gas may also beintroduced into the reactor. The reaction gas may be an oxidizing agentsuch as O₂; O₃; H₂O; H₂O₂; oxygen containing radicals such as O. or OH.;NO; NO₂; carboxylic acids such as formic acid, acetic acid, propionicacid; radical species of NO, NO₂, or the carboxylic acids;para-formaldehyde; and mixtures thereof. Preferably, the oxidizing agentis selected from the group consisting of O₂, O₃, H₂O, H₂O₂, oxygencontaining radicals thereof such as O. or OH., and mixtures thereof.Preferably, when an ALD process is performed, the co-reactant is plasmatreated oxygen, ozone, or combinations thereof. When an oxidizing gas isused, the resulting silicon containing film will also contain oxygen.

Alternatively, the reaction gas may be a reducing agent such as one ofH₂, NH₃, (SiH₃)₃N, hydridosilanes (such as SiH₄, Si₂H₆, Si₃H₈, Si₄H₁₀,Si₅H₁₀, Si₆H₁₂), chlorosilanes and chloropolysilanes (such as SiHCl₃,SiH₂Cl₂, SiH₃Cl, Si₂Cl₆, Si₂HCl₅, Si₃Cl₈), alkysilanes (such as Me₂SiH₂,Et₂SiH₂, MeSiH₃, EtSiH₃), hydrazines (such as N₂H₄, MeHNNH₂, MeHNNHMe),organic amines (such as NMeH₂, NEtH₂, NMe₂H, NEt₂H, NMe₃, NEt₃,(SiMe₃)₂NH), diamines such as ethylene diamine, dimethylethylenediamine, tetramethylethylene diamine, pyrazoline, pyridine, B-containingmolecules (such as B₂H₆, trimethylboron, triethylboron, borazine,substituted borazine, dialkylaminoboranes), alkyl metals (such astrimethylaluminum, triethylaluminum, dimethylzinc, diethylzinc), radicalspecies thereof, or mixtures thereof. When a reducing agent is used, theresulting silicon containing film may be pure Si.

Alternatively, the reaction gas may be selected from the groupconsisting of H₂, NH₃, SiH₄, Si₂H₆, Si₃H₈, SiH₂Me₂, SiH₂Et₂, N(SiH₃)₃,hydrogen radicals thereof, and mixtures thereof.

Alternatively, the reaction gas may be HCDS or PCDS.

Alternatively, the reaction gas may be a hydrocarbon, saturated orunsaturated, linear, branched or cyclic, such as but not limited toethylene, acetylene, propylene, isoprene, cyclohexane, cyclohexene,cyclohexadiene, pentene, pentyne, cyclopentane, butadiene, cyclobutane,terpinene, octane, octane, or combinations thereof.

The reaction gas may be treated by a plasma, in order to decompose thereaction gas into its radical form. N₂ may also be utilized as areducing agent when treated with plasma. For instance, the plasma may begenerated with a power ranging from about 50 W to about 500 W,preferably from about 100 W to about 200 W. The plasma may be generatedor present within the reactor itself. Alternatively, the plasma maygenerally be at a location removed from the reactor, for instance, in aremotely located plasma system. One of skill in the art will recognizemethods and apparatus suitable for such plasma treatment.

The desired silicon-containing film also contains another element, suchas, for example and without limitation, B, Zr, Hf, Ti, Nb, V, Ta, Al,Si, Ge.

The disclosed Si-containing film forming compositions may also be usedwith a halosilane or polyhalodisilane or polyhalotrisilane, such ashexachlorodisilane, pentachlorodisilane, or tetrachlorodisilane, oroctachlorotrisilane, and one or more co-reactant gases to form SiN orSiCN films, as disclosed in PCT Publication Number WO2011/123792, theentire contents of which are incorporated herein in their entireties.

The vapor of the Si-containing film forming composition and one or moreco-reactants may be introduced into the reaction chamber simultaneously(chemical vapor deposition), sequentially (atomic layer deposition), orin other combinations. For example, the Si-containing film formingcomposition may be introduced in one pulse and two additional metalsources may be introduced together in a separate pulse (modified atomiclayer deposition). Alternatively, the reaction chamber may alreadycontain the co-reactant prior to introduction of the Si-containing filmforming composition. The co-reactant may be passed through a plasmasystem localized or remotely from the reaction chamber, and decomposedto radicals, like in the flowable CVD configuration. Alternatively, theSi-containing film forming composition may be introduced to the reactionchamber continuously while other precursors or reactants are introducedby pulse (pulsed-chemical vapor deposition). In another alternative, theSi-containing film forming composition and one or more co-reactants maybe simultaneously sprayed from a shower head under which a susceptorholding several wafers is spun (spatial ALD).

In one non-limiting exemplary atomic layer deposition process, the vaporphase of the Si-containing film forming composition is introduced intothe reaction chamber, where it is contacted with a suitable substrate.Excess composition may then be removed from the reaction chamber bypurging and/or evacuating the reaction chamber. An oxygen source isintroduced into the reaction chamber where it reacts with the absorbedcarbosilazane or polycarbosilazane precursor in a self-limiting manner.Any excess oxygen source is removed from the reaction chamber by purgingand/or evacuating the reaction chamber. If the desired film is a siliconoxide film, this two-step process may provide the desired film thicknessor may be repeated until a film having the necessary thickness has beenobtained.

Alternatively, if the desired film is a silicon metal/metalloid oxidefilm (i.e., SiMO_(x), wherein x may be 0-4 and M is B, Zr, Hf, Ti, Nb,V, Ta, Al, Si, Ge, or combinations thereof), the two-step process abovemay be followed by introduction of a vapor of a metal- ormetalloid-containing precursor into the reaction chamber. The metal- ormetalloid-containing precursor will be selected based on the nature ofthe silicon metal/metalloid oxide film being deposited. Afterintroduction into the reaction chamber, the metal- ormetalloid-containing precursor is contacted with the substrate. Anyexcess metal- or metalloid-containing precursor is removed from thereaction chamber by purging and/or evacuating the reaction chamber. Onceagain, an oxygen source may be introduced into the reaction chamber toreact with the metal- or metalloid-containing precursor. Excess oxygensource is removed from the reaction chamber by purging and/or evacuatingthe reaction chamber. If a desired film thickness has been achieved, theprocess may be terminated. However, if a thicker film is desired, theentire four-step process may be repeated. By alternating the provisionof the Si-containing film forming composition, metal- ormetalloid-containing precursor, and oxygen source, a film of desiredcomposition and thickness can be deposited.

Additionally, by varying the number of pulses, films having a desiredstoichiometric M:Si ratio may be obtained. For example, a SiMO₂ film maybe obtained by having one pulse of the Si-containing film formingcomposition and one pulse of the metal- or metalloid-containingprecursor, with each pulse being followed by a pulse of the oxygensource. However, one of ordinary skill in the art will recognize thatthe number of pulses required to obtain the desired film may not beidentical to the stoichiometric ratio of the resulting film.

In another alternative, Si or dense SiCN films may be deposited via anALD or modified plasma-enhanced ALD process using the disclosedcompositions and an N-containing co-reactant like ammonia, N₂, N₂/H₂mixture, or an amine. For N₂ and N₂/H₂ mixture, the co-reactant needs tobe activated by a plasma, either direct (within the chamber) or remote.

In yet another alternative, a silicon-containing film may be depositedby the flowable PECVD (f-PECVD) method disclosed in U.S. Pat. App. Pub.No. 2014/0051264 using the disclosed Si-containing film formingcompositions and a radical nitrogen- or oxygen-containing co-reactant.The radical nitrogen- or oxygen-containing co-reactant, such as NH₃ orH₂O respectively, is generated in a remote plasma system. The radicalco-reactant and the vapor phase of the disclosed compositions areintroduced into the reaction chamber where they react and deposit theinitially flowable film on the substrate. Applicants believe that thenitrogen atom of the disclosed compounds help to further improve theflowability of the deposited film, resulting in films having less voidsthan those produced by other precursors. Applicants believe that thefilms deposited using the disclosed Si-containing film formingcompositions in a flowable CVD process with NH₃ plasma will produce aSiCN film having desired etching selectivity with respect to siliconoxide films due to the precursor's Si—C—Si backbone providing a filmhaving sufficient C content.

In yet another embodiment, the flowable film can be deposited solely bycondensation (Thermal flowable CVD, or T-FCVD) by holding the wafer to atemperature lower than the dew point of the precursor at the partialpressure of the precursor in the chamber. For such applications, havinga low vapor pressure precursor (typically<50 torr at room temperature,and even preferably <10 torr at room temperature) is beneficial tofacilitate the precursor condensation without chilling the wafer to verylow temperature. The substituted or unsubstituted N(DSP)₃ and RN(DSP)₂family of molecules have a suitable range of volatility. The crosslinking of such films may then be achieved in-situ or ex-situ by one orseveral of various means, including but not limited to exposure of thedeposited film to a reactive gas, to plasma, to photons, to an electronbeam, to a neutral particle beam, or to a catalyst. The catalyst may bepre-deposited, co-deposited or post-deposited, and may be activated bymeans such as heating or photon exposure. Chemically speaking, suchcross-linking can be achieved by a variety of chemical reactions rangingfrom but not restricted to Si—H/N—H H₂ elimination, hydrosilylation,silazane formation by condensation of amine groups, siloxane formationby condensation of silanol groups, ring opening polymerisation, and/ordehydrogenative coupling.

Also disclosed are methods of using the disclosed precursors presentedin Formula (I) or (II) in coating deposition methods, such as spincoating, spray coating, dip coating or slit coating techniques. To besuitable for coating methods, the disclosed precursors should have amolecular weight ranging from approximately 500 to approximately1,000,000, preferably from approximately 1,000 to approximately 100,000,and more preferably from approximately 3,000 to approximately 50,000.The disclosed methods provide for the use of the Si-containing filmforming composition for deposition of silicon-containing films. Thedisclosed methods may be useful in the manufacture of semiconductor,photovoltaic, LCD-TFT, optical coatings, or flat panel type devices. Themethod includes: applying the liquid form of the disclosed Si-containingfilm forming composition on a substrate and curing to form theSi-containing layer on the substrate.

As discussed previously, the liquid form of the disclosed Si-containingfilm forming composition may be a neat solution of the precursor or amixture of the precursor with a volatile solvent and optional crosslinking initiators such as radical generators (thermal orphoto-initiated) and catalysts. Thermally activated (peroxides or azacompounds) or UV initiated (for instance phenones, or quinones) radicalinitiators may be included in the Si-containing film formingcomposition. Catalysts that promote cross linking of the film upon UVactivation or/and heating may also be included in the film-formingcomposition. Such catalysts include photo-acid generators, Lewis acidsand typical hydrosilylation catalysts. Among such compounds, B(C₆F₅)₃ isa particularly suitable compound, as it is a Lewis acid and a strongdehydrogenative catalyst.

Exemplary coating deposition methods include spin-coating. FIG. 1provide a flow chart of an exemplary spin-coating process. One ofordinary skill in the art will recognize that fewer or additional stepsthan those provided in FIG. 1 may be performed without departing fromthe teachings herein. For example, the characterization step utilized ina R&D setting may not be required in commercial operations. One ofordinary skill in the art will further recognize that the process ispreferably performed under an inert atmosphere to prevent undesiredoxidation of the film and/or in a clean room to help preventcontamination to prevent particle contamination of the film.

The planar or patterned substrate on which the Si-containing film is tobe deposited may be prepared for the deposition process in Steps 1-4.High purity gases and solvents are used in the preparation process.Gases are typically of semiconductor grade and free of particlecontamination. For semiconductor usage, solvents should be particlefree, typically less than 100 particle/mL (0.5 μm particle, morepreferably less than 10 particles/mL) and free of non-volatile residuesthat would lead to surface contamination. Semiconductor grade solventshaving less than 50 ppb metal contamination (for each element, andpreferably less than 5 ppb) are advised.

In Step 1, the substrate is sonicated in acetone at room temperature(between approximately 20° C. and approximately 25° C.) forapproximately 60 second to approximately 120 seconds, and preferably forapproximately 90 seconds. In Step 2, the planar or patterned substrateis sonicated at room temperature in isopropyl acohol (IPA) forapproximately 60 second to approximately 120 seconds, and preferably forapproximately 90 seconds. One of ordinary skill in the art willrecognize that these steps may be performed in the same or differentsonicators. Different sonicaters require more equipment, but provide aneasier process. The sonicator must be thoroughly cleaned between Step 1and 2 if used for both to prevent any contamination of the substrate.Exemplary sonicators suitable for the disclosed methods include LeelaElectronics Leela Sonic Models 50, 60, 100, 150, 200, 250, or 500 orBranson's B Series. In Step 3, the substrate is removed from the IPAsonicator and rinsed with fresh IPA. In Step 4, the rinsed substrate isdried using an inert gas, such as N₂ or Ar. One of ordinary skill in theart will recognize that Steps 1 through 4 provide one exemplary waferpreparation process. Multiple wafer preparation processes exist and maybe utilized without departing from the teachings herein. See, e.g.,Handbook of Silicon Wafer Cleaning Technology, 3^(rd) Edition, 2017(William Andrew). For example, an UV/ozonation process may be used if amore hydrophilic surface is desired. One of ordinary skill in the artmay determine the appropriate wafer preparation process based at leastupon the substrate material and degree of cleanliness required.

After this 4 step preparation, the substrate is transferred to the spincoater. Exemplary suitable spin coaters include Brewer Science's Cee®Precision spin coaters, Laurell's 650 series spin coaters, SpecialtyCoating System's G3 spin coaters, or Tokyo Electron's CLEAN TRACK ACTequipment family. Any of the Si-containing film forming compositionsdisclosed above, but preferably those of Formula II, are dispensed ontothe substrate in Step 5 and the wafer is spun in Step 6. One of ordinaryskill in the art will recognize that Step 5 and Step 6 may be performedsequentially (static mode) or concurrently (dynamic mode). Step 5 isperformed using a manual or auto-dispensing device (such as a pipette,syringe, or liquid flow meter). When Steps 5 and 6 are performedconcurrently, the initial spin rate is slow (i.e., between approximately5 rpm to approximately 999 rpm, preferably between approximately 5 rpmto approximately 300 rpm). After all of the Si-containing film formingcomposition is dispensed (i.e., when Step 5 is complete in either staticor dynamic mode), the spin rate ranges between approximately 1000 rpm toapproximately 4000 rpm. The wafer is spun until a uniform coating isachieved across the substrate, which typically takes betweenapproximately 10 seconds and 3 approximately minutes. Steps 5 and 6produce a Si-containing film on the wafer. One of ordinary skill in theart will recognize tha thte required duration of the spin coatingprocess, the acceleration rate, the solvent evaporation rate, etc., areadjustable parameters that require optimization for each new formulationin order to obtain the target film thickness and uniformity (see, e.g.,University of Louisville, Micro/Nano Technology Center—Spin CoatingTheory, October 2013).

After the Si-containing film is formed, the wafer is pre-baked or softbaked in Step 7 to remove any remaining volatile organic components ofthe Si-containing film forming composition and/or by-products from thespin-coating process. Step 7 may take place in a thermal chamber or on ahot plate at a temperature ranging from approximately 25° C. toapproximately 200° C. for a time period ranging from approximately 1minute to approximately 120 minutes. Exemplary hot plates include BrewerScience's Cee® Model 10 or 11 or Polos' precision bake plates.

In step 8, the the substrate is cured to produce the desired dielectricmaterial. 3 non-limiting options are shown in FIG. 1. Any of the 3options may be performed using an inert or reactive gas. Exemplary inertgases include N₂, Ar, He, KR, Xe, etc. The reactive gas may be used tointroduce oxygen, nitrogen, or carbon into the film. Exemplary reactivegases that introduce oxygen into the film include oxygen-containinggases, such as O₂, O₃, air, H₂O, H₂O₂, etc. Exemplary reactive gasesthat introduce nitrogen into the film include nitrogen-containing gases,such as NH₃; NR₃, wherein R is a C1-C4 hydrocarbon; etc. Exemplaryreactive gases that introduce carbon into the film includecarbon-containing gases, and specifically unsaturated carbon-containinggases, such as alcenes and alcynes (ethylene, acetylene, propylene,etc.).

In Step 8a, the substrate is subject to thermal curing at a temperatureranging from approximately 101° C. to approximately 1,000° C.,preferably from approximately 200° C. to approximately 800° C. under aninert or reactive gas. A furnace or rapid thermal processor may be usedto perform the thermal curing process. Exemplary furnaces include theThermoFisher Lindberg/Blue M™ tube furnace, the Thermo ScientificThermolyne™ benchtop tube furnace or muffle furnace, the Inseto tabletopquartz tube furnace, the NeyTech Vulcan benchtop furnace, the TokyoElectron TELINDY™ thermal processing equipment, or the ASM InternationalADVANCE® vertical furnace. Exemplary rapid thermal processors includeSolaris 100, ULVAC RTP-6, or Annealsys As-one 100.

Alternatively, in Step 8b, the substrate is subject to UV-curing at awavelength ranging from approximately 190 nm to approximately 400 nmusing a monochromatic or polychromatic source. Exemplary VUV- orUV-curing systems suitable to perform Step 8b include, but are notlimited to, the Nordson Coolwaves® 2 UV curing system, the HeraeusNoblelight Light Hammer® 10 product platform, or the Radium Xeradex®lamp.

In another alternative, both the thermal and UV process may be performedat the same temperature and wavelength criteria specified for Steps 8aand 8b. One of ordinary skill in the art will recognize that the choiceof curing methods and conditions will be determined by the targetsilicon-containing film desired.

In Step 9, the cured film is characterized using standard analytictools. Exemplary tools include, but are not limited to, ellipsometers,x-ray photoelectron spectroscopy, atomic force microscopy, x-rayfluorescence, fourier-transform infrared spectroscopy, scanning electronmicroscopy, secondary ion mass spectrometry (SIMS), Rutherfordbackscattering spectrometry (RBS), profilometer for stress analysis, orcombination thereof.

The liquid form of the disclosed Si-containing film forming compositionmay be applied directly to the center of the substrate and then spreadto the entire substrate by spinning or may be applied to the entiresubstrate by spraying. When applied directly to the center of thesubstrate, the substrate may be spun to utilize centrifugal forces toevenly distribute the composition over the substrate. Alternatively, thesubstrate may be dipped in the Si-containing film forming composition.The resulting film may be dried at room temperature for a period of timeto vaporize the solvent or volatile components of the film or dried byforce-drying or baking or by the use of one or a combination of anyfollowing suitable process including thermal curing and irradiations,such as, ion irritation, electron irradiation, UV and/or visible lightirradiation, etc.

The disclosed carbosilazane precursors in the Si-containing film formingcompositions may prove useful as monomers for the synthesis ofcarbosilazane containing polymers. The Si-containing film formingcompositions may be used to form spin-on dielectric film formulations,for lithographic applications (tone inversion layers for instance), orfor anti-reflective films. For example, the disclosed Si-containing filmforming compositions may be included in a solvent and applied to asubstrate to form a film. If necessary, the substrate may be rotated toevenly distribute the Si-containing film forming composition across thesubstrate. One of ordinary skill in the art will recognize that theviscosity of the Si-containing film forming compositions will contributeas to whether rotation of the substrate is necessary. The resulting filmmay be heated under an inert gas, such as Argon, Helium, or nitrogenand/or under reduced pressure. Alternatively, the resulting film may beheated under a reactive gas like NH₃ or hydrazine to enhance theconnectivity and nitridation of the film. Electron beams or ultravioletradiation may be applied to the resulting film. The reactive groups ofthe disclosed carbosilazane or polycarbosilazane precursors (i.e., thedirect Si—N, N—H or Si—H bonds) may prove useful to increase theconnectivity of the polymer obtained.

The silicon-containing films resulting from the processes discussedabove may include SiO₂; SiC; SiN; SiON; SiOC; SiONC; SiBN; SiBCN; SiCN;SiMCO, in which M is selected from Zr, Hf, Ti, Nb, V, Ta, Al, Ge,depending of course on the oxidation state of M. One of ordinary skillin the art will recognize that by judicial selection of the appropriateSi-containing film forming composition nd co-reactants, the desired filmcomposition may be obtained.

Upon obtaining a desired film thickness, the film may be subject tofurther processing, such as thermal annealing, furnace-annealing, rapidthermal annealing, UV or e-beam curing, and/or plasma gas exposure.Those skilled in the art recognize the systems and methods utilized toperform these additional processing steps. For example, thesilicon-containing film may be exposed to a temperature ranging fromapproximately 200° C. and approximately 1000° C. for a time ranging fromapproximately 0.1 second to approximately 7200 seconds under an inertatmosphere, a H-containing atmosphere, a N-containing atmosphere, orcombinations thereof. Most preferably, the temperature is 600° C. forless than 3600 seconds. Even more preferably, the temperature is lessthan 400° C. The annealing step may be performed in the same reactionchamber in which the deposition process is performed. Alternatively, thesubstrate may be removed from the reaction chamber, with theannealing/flash annealing process being performed in a separateapparatus. Any of the above post-treatment methods, but especiallyUV-curing, has been found effective to enhance the connectivity andcross linking of the film. Typically, a combination of thermal annealingto <400° C. (preferably about 100° C.-300° C.) and UV curing is used toobtain the film with the highest density.

EXAMPLES

The following non-limiting examples are provided to further illustrateembodiments of the invention. However, the examples are not intended tobe all inclusive and are not intended to limit the scope of theinventions described herein.

Example 1 Syntheses of Starting Materials 1,2-disilapropane (DSP) and1,3-disilabutane (DSB)

3LiAlH₄+2SiCl₃CH₂SiCl₃→2DSP+3LiAlCl₄

3LiAlH₄+2SiCl₃CH₂CH₂SiCl₃→2DSB+3LiAlCl₄

Lithium aluminium hydride LiAlH₄ (LAH) was placed into a 4 L vesselequipped with a mechanical stirrer under inert atmosphere. The vesselwas cooled to −78° C., and then 1 L of cold (ca. −30° C.) diglyme(H₃COC₂H₄OC₂H₄OCH₃) for DSP or di-nbutyl ether (H₉C₄OC₄H₉) for DSB wasslowly added to the vessel. The mixture in the vessel was allowed towarm to −10° C. while stirring. 1,2-bis(trichlorosilyl)methaneSiCl₃CH₂SiCl₃ or 1,2-bis(trichlorosilyl)ethane SiCl₃CH₂CH₂SiCl₃ wasadded dropwise to the warmed mixture, while preventing the reactionmixture from getting warmer than 20° C. After the addition, the mixturewas warmed to 25° C. and stirred for 2 hours. The volatile DSP or DSBwas condensed into a trap (−78° C.) at 30° C. DSP was isolated in 82%yield, 96% purity shown by Gas Chromatography (GC). DSB was isolated ascolorless liquid. Yield 65%, 98.8% purity shown by GC.

Example 2 Halogen-free route syntheses of bis(disilapropane)amineHN(SiH₂—CH₂—SiH₃)₂ (HN(DSP)₂) and tris((silylmethyl)silyl)amineN(SiH₂—CH₂—SiH₃)₃ (N(DSP)₃)

H₃Si—CH₂—SiH₃+NH₃→HN(DSP)₂

H₃Si—CH₂—SiH₃+NH₃→N(DSP)₃

Disilapropane and ammonia were catalyzed by Platinum on Carbon in apressure reactor to produce HN(DSP)₂ and N(DSP)₃. This is a halogen freeroute. The 0.3 L autoclave was equipped with a mechanical stirrer,thermocouple, pressure gauge, pressure transducer, and 3 meteringvalves. 10 (0.5 g/2.56 mol of Platinum) of 5 weight Platinum on carboncatalyst was added to the autoclave. The reactor was subsequently heatedsteadily under dynamic vacuum to 140° C. and held at this temperaturefor 3 hr. After cooling down to room temperature, the reactor waspressurized with helium (800 torr). Pentane (50 mL) was introduced intothe reactor in the glove box. After immersion of the reactor in a liquidnitrogen bath, atmospheric nitrogen was removed under vacuum. Ammonia (3g, 0.176 mol) and disilapropane (53.7 g, 0.705 mol) were transferred tothe reactor. The reactor was then heated to 50° C. After stirring at 457rpm for 30 hr, a pressure increase of approximately 486 psi was observedafter cooling to room temperature. Volatile components of the reactorcontents were cryotrapped in a stainless steel lecture bottle (SSLB)down to a pressure of 10 Torr. Analysis of the reactor contents byliquid inject GCMS revealed a 7:1 mixture of HN(DSP)₂ and N(DSP)₃together with minor higher boiling components. FIG. 1 is a GCMS spectrumof the final product of the N(DSP)₂ and N(DSP)₃ mixture produced.

The mixture was subject to a vacuum Fractional Distillation. The 1^(st)fraction (42° C./153 mtorr) comprised HN(DSP)₂(2.05 g, 6%) measured byGCMS. FIG. 2 is a GCMS spectrum of the the 1^(st) fraction, showing aHN(DSP)₂ and N(DSP)₃ mixture. The 2^(nd) fraction comprised a 14:1mixture of N(DSP)₃ and HN(DSP)₂ together with a higher boiling component(1.48 g) measured by GCMS. FIG. 3 is a GCMS spectrum 2^(nd) fraction,showing the mixture of N(DSP)₃ and HN(DSP)₂.

Example 3 Halogen Free Route Syntheses of NDSP Oligomers[—NH—SiH₂—CH₂—SiH₂—]_(n) ([NH-DSP]_(n)) and[—N(SiH₂—CH₂—SiH₃)—SiH₂—CH₂—SiH₂]_(n) ([—N(DSP)-DSP]_(n)) (n=2 to 400)

H₃Si—CH₂—SiH₃+NH₃→HNDSP2→[—NH-DSP-]_(n)

H₃Si—CH₂—SiH₃+NH₃→NDSP3→[—N(DSP)-DSP—]_(n)

Synthesis of NDSP oligomer was catalyzed by Platinum on Carbon andperformed in a pressure reactor by the reaction between disilapropaneand ammonia. The reaction is the same as these systheses of HNDSP2 andNDSP3, which is also a halogen free route. Referring to Example 2, whenthe reagents in Example 2 were overcooked, colorless viscous oil wasleft in the distillation pot (7.5 g) after removal of HNDSP2 and NDSP3from the products by the vacuum Fractional Distillation.

FIG. 4 is a GPC spectrum of the colorless viscous oil after removal ofHNDSP2 and NDSP3 produced by halogen free route. This viscous oil wasanalyzed by gel permeation chromatography (GPC) and, as shown in FIG. 4,a distribution ranging from 26,000 to 500 Daltons was evident, showingthe major components have high molecular weight oligomers or polymerswhich are linear or branched oligomer [—NH-DSP-]_(n) or[—N(DSP)-DSP-]_(n) formed by DSP. The calculated molecular weightaverages and polydispersity index for the oiligomer are shown in Table2.

TABLE 2 calculated molecular weight averages and polydispersity index ofthe oilgomer Mn Mw Mz PDI Sample ID (Daltons) (Daltons) (Daltons)(Mw/Mn) SK-586-89-3 Colorless 1,440 2,230 3,670 1.5 oil SK586-96-1Colorless 8,340 95,700 1,190,000 11.5 oil in THF

Example 4 Selective Synthesis of HNDSP2

ClSiH₂—CH₂—SiH₃+NH₃→HNDSP2+HCl

After purging with N₂, a two liter 3-neck flask is charged with anon-polar solvent, which was anhydrous toluene in this process.Chlorosilylmethylsilane (DSP-Cl) (53.6 g, 0.48 mol) was added to theflask by dripping into the flask. NH₃ (11 g, 0.65 mol) at +5° C. wasslowly added by bubbling into the mixture in the flask. After therequired amount of NH₃ was added, the mixture was warmed to roomtemperature and stirred for 16 hours. Formation of white solids in aclear liquid was observed. The reaction mixture was then transferred viacannula to a schlenk filter funnel equipped with an air-free filterfrit. The filtrate solid was washed with anhydrous toluene for 4 times.FIG. 5a is a GC spectrum of the product after stirring for 16 hours(overnight or ON) at room temperature. FIG. 5b is GC spectrum of thefinal product after 8 weeks at room temperature. In the figures, CATOrepresents the reactant DSP-Cl and NDSP3 represents a possibleby-product. As shown in FIG. 5a , the final product contains almost 100%HNDSP2 comparing to NDSP3. As shown in FIG. 5b , very little NDSP3 wasproduced after 8 weeks. Thus, this synthesis method provides the methodto selectively produce HNDSP2 without by-product NDSP3.

Example 5 Selective synthesis of NDSP3

3ClSiH₂—CH₂—SiH₃+4NH₃→NDSP3+3NH₄Cl

Replacing non-polar solvent toluene with a polar solvent, such as THF,in Example 4, NDSP3 was selectively produced without by-product HNDSP2.

It will be understood that many additional changes in the details,materials, steps, and arrangement of parts, which have been hereindescribed and illustrated in order to explain the nature of theinvention, may be made by those skilled in the art within the principleand scope of the invention as expressed in the appended claims. Thus,the present invention is not intended to be limited to the specificembodiments in the examples given above and/or the attached drawings.

1. A Si-containing film forming composition comprising a precursorcontaining a unit having the formula:[—NR—R⁴R⁵Si—(CH₂)_(t)—SiR²R³—]_(n)   (II) wherein t=1 to 4; n=2 to 400;R², R³, R⁴, and R⁵ are independently H, a C₁ to C₆ hydrocarbon, or analkylamino group having the formula NR″₂ and each R″ is independently H,a C₁-C₆ hydrocarbon, a C₆-C₁₂ aryl, or NR″₂ forms a cyclic amine group,and provided that at least one of R², R³, R⁴, and R⁵ is H; and R is H; aC₁-C₆ hydrocarbon; a silyl group having the formula SixR′_(2x+1), withx=1 to 4 and each R′ independently ═H, a C₁-C₆ hydrocarbon group, or analkylamino group having the formula NR″₂ and each R″ independently H, aC₁-C₆ group, a C₆-C₁₂ aryl, or NR″₂ forms a cyclic amine group; or aR^(1′)R^(2′)R^(3′)Si—(CH₂)_(b)SiR^(4′)R^(5′) group, with b=1 to 2 andR^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) are independently a H, aC₁-C₆ hydrocarbon, a C₆-C₁₂ aryl, or an alkylamino group having theformula NR″₂ and each R″ is independently H, a C₁-C₆ group, a C₆-C₁₂aryl, or NR″₂ forms a cyclic amine group; and provided that at least oneof R^(1′), R^(2′), R^(3′), R^(4′), and R^(5′) is H.
 2. The Si-containingfilm forming composition of claim 1, wherein the precursor contains aunit having the formula [—NH—SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2. 3.The Si-containing film forming composition of claim 1, wherein theprecursor contains a unit having a formula selected from the groupconsisting of: [—N(SiH₃)—SiH₂(CH₂)_(t)—SiH₂—]_(n),[—N(Si₂H₅)—SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si₃H₇)—SiH₂—(CH₂)_(t)—SiH₂—]_(n), and[—N(Si₄H₉)—SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 4. The Si-containingfilm forming composition of claim 1, wherein the precursor contains aunit having a formula selected from the group consisting of[—N(Si(Me)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(Et)₃-SiH₂—(CH₂)_(t)——SiH₂—]_(n),[—N(Si(iPr)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(nPr)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(Bu)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(iBu)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(tBu)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(amyl)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(hexyl)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[Nx(SiH(Me)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(Et)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(iPr)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(nPr)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(Bu)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(iBu)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(tBu)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(amyl)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(hexyl)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(Me)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(Et)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(iPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(nPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(Bu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(iBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(tBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(amyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), and[—N(SiH₂(hexyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 5. TheSi-containing film forming composition of claim 1, wherein the precursorcontains a unit having a formula selected from the group consisting of[—N(SiH₂—CH₂—SiH₃)—SiH₂(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂—CH₂—CH₂—SiH₃)—(CH₂)_(t)—CH₂SiH₂—]_(n),[—N(SiMe₃-CH₂—SiMe₂)—(CH₂)_(t)—CH₂—SiH₂—]_(n),[—N(SiMe₃-CH₂—CH₂—SiMe₂)SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiEt₃-CH₂—SiEt₂)SiH₂—(CH₂)_(t)—SiH₂—]_(n), and[—N(SiEt₃-CH₂—CH₂—SiEt₂)SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 6. TheSi-containing film forming composition of claim 1, wherein the precursorcontains a unit having a formula selected from the group consisting of[—N(Me)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(Et)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(iPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(nPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Bu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(iBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(tBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(amyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),and [—N(hexyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 7. TheSi-containing film forming composition of claim 1, wherein the precursorcontains a unit having a formula selected from the group consisting of[—N(SiH₂NMe₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂NEt₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂—NiPr₂)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂NnPr₂)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂NMeEt)-H₂Si—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(NMe₂)₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n), and[—N(SiH(NEt₂)₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 8. TheSi-containing film forming composition of claim 1, wherein the precursorcontains a unit having a formula selected from the group consisting of[—NH—H₂Si—(CH₂)_(t)—SiH(CH₂═CH₂)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(CH₂—CH₂═CH₂)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NH₂)—]_(n), [—NH—H₂Si—(CH₂)_(t)—SiH(NMe₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NMeEt)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NEt₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NnPr₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiPr₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NBu₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiBu₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NtBu₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NAm₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NCyPentyl₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(Nhexyl₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NCyHex₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NMeH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NEtH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NnPrH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiPrH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NBuH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiBuH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NtBuH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NAmH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(pyridine)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(pyrrole)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(pyrrolidine)-]_(n), and[—NH—H₂Si—(CH₂)_(t)—SiH(imidazole)-]_(n), with t=1-2.
 9. TheSi-containing film forming composition of claim 1, wherein the precursorcontains a unit having a formula selected from the group consisting of[—NH—H₂Si—(CH₂)_(t)—Si(CH₂═CH₂)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(CH₂—CH₂═CH₂)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NH₂)₂—]_(n), [—NH—H₂Si—(CH₂)_(t)—Si(NMe₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NMeEt)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NEt₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NnPr₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiPr₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NBu₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiBu₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NtBu₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NAm₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NCyPentyl₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(Si(Nhexyl₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NCyHex₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NMeH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NEtH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NnPrH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiPrH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NBuH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiBuH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NtBuH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NAmH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(pyridine)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(pyrrole)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(pyrrolidine)₂-]_(n), and[—NH—H₂Si—(CH₂)_(t)—Si(imidazole)₂-]_(n), with t=1-2.
 10. TheSi-containing film forming composition of claim 1, wherein the precursorcontains a unit having a formula selected from the group consisting of[—NH—SiH(CH₂═CH₂)—(CH₂)_(t)—SiH(CH₂═CH₂)—]_(n),[—NH—SiH(CH₂—CH₂═CH₂)—(CH₂)_(t)—SiH(CH₂—CH₂═CH₂)—]_(n),[—NH—SiH(NH₂)—(CH₂)_(t)—SiH(NH₂)—]_(n),[—NH—SiH(NMe₂)—(CH₂)_(t)—SiH(NMe₂)-]_(n),[—NH—SiH(NMeEt)-(CH₂)_(t)—SiH(NMeEt)-]_(n),[—NH—SiH(NEt₂)-(CH₂)_(t)—SiH(NEt₂)-]_(n),[—NH—SiH(NnPr₂)-(CH₂)_(t)—SiH(NnPr₂)-]_(n),[—NH—SiH(NiPr₂)-(CH₂)_(t)—SiH(NiPr₂)-]_(n),[—NH—SiH(NBu₂)-(CH₂)_(t)—SiH(NBu₂)-]_(n),[—NH—SiH(NiBu₂)-(CH₂)_(t)—SiH(NiBu₂)-]_(n),[—NH—SiH(NtBu₂)-(CH₂)_(t)—SiH(NtBu₂)-]_(n),[—NH—SiH(NAm₂)-(CH₂)_(t)—SiH(NAm₂)-]_(n),[—NH—SiH(NCyPentyl₂)-(CH₂)_(t)—SiH(NCyPentyl₂)-]_(n),[—NH—SiH(Nhexyl₂)-(CH₂)_(t)—SiH(Nhexyl₂)-]_(n),[—NH—SiH(NCyHex₂)-(CH₂)_(t)—SiH(NCyHex₂)-]_(n),[—NH—SiH(NMeH)—(CH₂)_(t)—SiH(NMeH)—]_(n),[—NH—SiH(NEtH)—(CH₂)_(t)—SiH(NEtH)—]_(n),[—NH—SiH(NnPrH)—(CH₂)_(t)—SiH(NnPrH)—]_(n),[—NH—SiH(NiPrH)—(CH₂)_(t)—SiH(NiPrH)—]_(n),[—NH—SiH(NBuH)—(CH₂)_(t)—SiH(NBuH)—]_(n),[—NH—SiH(NiBuH)—(CH₂)_(t)—SiH(NiBuH)—]_(n),[—NH—SiH(NtBuH)—(CH₂)_(t)—SiH(NtBuH)—]_(n),[—NH—SiH(NAmH)—(CH₂)_(t)—SiH(NAmH)—]_(n),[—NH—SiH(pyridine)-(CH₂)_(t)—SiH(pyridine)-]_(n),[—NH—SiH(pyrrole)-(CH₂)_(t)—SiH(pyrrole)-]_(n),[—NH—SiH(pyrrolidine)-(CH₂)_(t)—SiH(pyrrolidine)-]_(n), and and[—NH—SiH(imidazole)-(CH₂)_(t)—SiH(imidazole)-]_(n), with t=1-2.
 11. Amethod of forming a Si-containing film on a substrate, the methodcomprising forming a solution comprising the Si-containing film formingcomposition of claim 1; and contacting the solution with the substratevia a spin coating, spray coating, dip coating, or slit coatingtechnique to form the Si-containing film.
 12. The method of claim 11,wherein the precursor contains a unit having the formula[—NH—SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 13. The method of claim 11,wherein the precursor contains a unit having a formula selected from thegroup consisting of: [—N(SiH₃)—SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si₂H₅)—SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si₃H₇)—SiH₂—(CH₂)_(t)—SiH₂—]_(n), and[—N(Si₄H₉)SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 14. The method of claim11, wherein the precursor contains a unit having a formula selected fromthe group consisting of [—N(Si(Me)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(Et)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(iPr)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(nPr)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(Bu)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(iBu)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(tBu)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(amyl)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Si(hexyl)₃-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—Nx(SiH(Me)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(Et)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(iPr)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(nPr)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(Bu)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(iBu)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(tBu)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(amyl)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(hexyl)₂-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(Me)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(Et)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(iPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(nPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(Bu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(iBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(tBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂(amyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), and[—N(SiH₂(hexyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 15. The method ofclaim 11, wherein the precursor contains a unit having a formulaselected from the group consisting of[—N(SiH₂—CH₂—SiH₃)—SiH₂(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂—CH₂—CH₂—SiH₃)—(CH₂)_(t)—CH₂SiH₂—]_(n),[—N(SiMe₃-CH₂—SiMe₂)—(CH₂)_(t)—CH₂SiH₂—]_(n),[—N(SiMe₃-CH₂—CH₂—SiMe₂)—SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiEt₃-CH₂—SiEt₂)—SiH₂—(CH₂)_(t)—SiH₂—]_(n), and[—N(SiEt₃-CH₂—CH₂—SiEt₂)—SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 16. Themethod of claim 11, wherein the precursor contains a unit having aformula selected from the group consisting of[—N(Me)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(Et)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(iPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(nPr)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(Bu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(iBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(tBu)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), [—N(amyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),and [—N(hexyl)-SiH₂—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 17. The method ofclaim 11, wherein the precursor contains a unit having a formulaselected from the group consisting of[—N(SiH₂NMe₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂NEt₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂—NiPr₂)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂NnPr₂)-SiH₂—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH₂NMeEt)-H₂Si—(CH₂)_(t)—SiH₂—]_(n),[—N(SiH(NMe₂)₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n), and[—N(SiH(NEt₂)₂)-H₂Si—(CH₂)_(t)—SiH₂—]_(n), with t=1-2.
 18. The method ofclaim 11, wherein the precursor contains a unit having a formulaselected from the group consisting of[—NH—H₂Si—(CH₂)_(t)—SiH(CH₂═CH₂)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(CH₂—CH₂═CH₂)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NH₂)—]_(n), [—NH—H₂Si—(CH₂)_(t)—SiH(NMe₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NMeEt)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NEt₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NnPr₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiPr₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NBu₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiBu₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NtBu₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NAm₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NCyPentyl₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(Nhexyl₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NCyHex₂)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NMeH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NEtH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NnPrH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiPrH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NBuH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NiBuH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NtBuH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(NAmH)—]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(pyridine)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(pyrrole)-]_(n),[—NH—H₂Si—(CH₂)_(t)—SiH(pyrrolidine)-]_(n), and[—NH—H₂Si—(CH₂)_(t)—SiH(imidazole)-]_(n), with t=1-2.
 19. The method ofclaim 11, wherein the precursor contains a unit having a formulaselected from the group consisting of[—NH—H₂Si—(CH₂)_(t)—Si(CH₂═CH₂)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(CH₂—CH₂═CH₂)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NH₂)₂—]_(n), [—NH—H₂Si—(CH₂)_(t)—Si(NMe₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NMeEt)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NEt₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NnPr₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiPr₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NBu₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiBu₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NtBu₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NAm₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NCyPentyl₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(Si(Nhexyl₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NCyHex₂)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NMeH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NEtH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NnPrH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiPrH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NBuH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NiBuH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NtBuH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(NAmH)₂—]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(pyridine)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(pyrrole)₂-]_(n),[—NH—H₂Si—(CH₂)_(t)—Si(pyrrolidine)₂-]_(n), and[—NH—H₂Si—(CH₂)_(t)—Si(imidazole)₂-]_(n), with t=1-2.
 20. The method ofclaim 11, wherein the precursor contains a unit having a formulaselected from the group consisting of[—NH—SiH(CH₂═CH₂)—(CH₂)_(t)—SiH(CH₂═CH₂)—]_(n),[—NH—SiH(CH₂—CH₂═CH₂)—(CH₂)_(t)—SiH(CH₂—CH₂═CH₂)—]_(n),[—NH—SiH(NH₂)—(CH₂)_(t)—SiH(NH₂)—]_(n),[—NH—SiH(NMe₂)—(CH₂)_(t)—SiH(NMe₂)-]_(n),[—NH—SiH(NMeEt)(CH₂)_(t)—SiH(NMeEt)-]_(n),[—NH—SiH(NEt₂)(CH₂)_(t)—SiH(NEt₂)-]_(n),[—NH—SiH(NnPr₂)-(CH₂)_(t)—SiH(NnPr₂)-]_(n),[—NH—SiH(NiPr₂)-(CH₂)_(t)—SiH(NiPr₂)-]_(n),[—NH—SiH(NBu₂)-(CH₂)_(t)—SiH(NBu₂)-]_(n),[—NH—SiH(NiBu₂)-(CH₂)_(t)—SiH(NiBu₂)-]_(n),[—NH—SiH(NtBu₂)-(CH₂)_(t)—SiH(NtBu₂)-]_(n),[—NH—SiH(NAm₂)-(CH₂)_(t)—SiH(NAm₂)-]_(n),[—NH—SiH(NCyPentyl₂)-(CH₂)_(t)—SiH(NCyPentyl₂)-]_(n),[—NH—SiH(Nhexyl₂)-(CH₂)_(t)—SiH(Nhexyl₂)-]_(n),[—NH—SiH(NCyHex₂)-(CH₂)_(t)—SiH(NCyHex₂)-]_(n),[—NH—SiH(NMeH)—(CH₂)_(t)—SiH(NMeH)—]_(n),[—NH—SiH(NEtH)—(CH₂)_(t)—SiH(NEtH)—]_(n),[—NH—SiH(NnPrH)—(CH₂)_(t)—SiH(NnPrH)—]_(n),[—NH—SiH(NiPrH)—(CH₂)_(t)—SiH(NiPrH)—]_(n),[—NH—SiH(NBuH)—(CH₂)_(t)—SiH(NBuH)—]_(n),[—NH—SiH(NiBuH)—(CH₂)_(t)—SiH(NiBuH)—]_(n),[—NH—SiH(NtBuH)—(CH₂)_(t)—SiH(NtBuH)—]_(n),[—NH—SiH(NAmH)—(CH₂)_(t)—SiH(NAmH)—]_(n),[—NH—SiH(pyridine)-(CH₂)_(t)—SiH(pyridine)-]_(n),[—NH—SiH(pyrrole)-(CH₂)_(t)—SiH(pyrrole)-]_(n),[—NH—SiH(pyrrolidine)-(CH₂)_(t)—SiH(pyrrolidine)-]_(n), and and[—NH—SiH(imidazole)-(CH₂)_(t)—SiH(imidazole)-]_(n), with t=1-2.